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Boron group

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Group → 13
↓ Period
2 Boron powder
5
B
3 title="Al, Aluminium" style="text-align:center; color:#000000; background-color:transparent; border:2px solid #6e6e8e; ;"| Aluminium metal
13
Al
4 title="Ga, Gallium" style="text-align:center; color:#000000; background-color:transparent; border:2px solid #6e6e8e; ;"| Gallium crystas
31
Ga
5 title="In, Indium" style="text-align:center; color:#000000; background-color:transparent; border:2px solid #6e6e8e; ;"| Ductile indium wire
49
In
6 title="Tl, Thallium" style="text-align:center; color:#000000; background-color:transparent; border:2px solid #6e6e8e; ;"| Thallium metal stored under argon atmosphere
81
Tl
7 113
Uut
Legend
colspan="2" style="text-align: center; border: 1px solid #AAAAAA; background:Template:Element color/Metalloids;"|Metalloid
colspan="2" style="text-align: center; border: 1px solid #AAAAAA; background:Template:Element color/Poor metals;"|Poor metal
colspan="2" style="text-align: center; border: 1px solid #AAAAAA; background:Template:Element color/Unknown chemical properties;"|Unknown chemical properties
colspan="2" style="text-align: center; border: Template:Element frame/Primordial;" |Primordial element
colspan="2" style="text-align: center; border: Template:Element frame/Synthetic;" |Synthetic
Boron group

The boron group is the series of elements in group 13 (IUPAC style) in the periodic table. The boron group consists of boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), and ununtrium (Uut).

The group has previously also been referred to as the earth metals and the triels, from the Latin tri, three, stemming from the naming convention of this group as Group IIIB. These elements are characterized by having three electrons in their outer energy levels (valence layers).[1]

Boron is considered a metalloid, and the rest are considered poor metals, although ununtrium is not confirmed to be a poor metal yet and might not be due to relativistic effects. Boron occurs sparsely probably because of disruption of its nucleus by bombardment with subatomic particles produced from natural radioactivity. Aluminum occurs widely on earth and in fact, it is the third most abundant element in the Earth's crust (8.3%).[2] Gallium is found in the earth with an abundance of 13 ppm. Indium is the 61st most abundant element in the earth's crust and thallium is found in moderate amounts throughout the planet. Ununtrium is never found in nature and thus it is termed a synthetic element.

The group 13 elements have been known to have biological roles in the ecosystem. Boron is a trace element in humans and essential in some plants. Lack of boron will cause bad symptoms. Too much boron is also a bad thing that can cause many symptoms. Aluminum has no biological role or significant toxicity and because of that is very safe. Indium and gallium can stimulate metabolism and gallium is credited with its ability to bind itself to iron proteins. Thallium is a very known and effective poison that kills when administered into the body by more than a tiny piece.[3]


Characteristics

Like other groups, the members of this family show patterns in its electron configuration, especially the outermost shells resulting in trends in chemical behavior:

Z Element No. of electrons/shell
5 boron 2, 3
13 aluminum 2, 8, 3
31 gallium 2, 8, 18, 3
49 indium 2, 8, 18, 18, 3
81 thallium 2, 8, 18, 32, 18, 3
113 ununtrium 2, 8, 18, 32, 32, 18, 3

The boron group is notable in its trends like the electron configuration as put above and by some of its elements' characteristics. Boron, though, is different from the other member's characteristics in factors such as its hardness, refractivity and unlikeness of participating in metallic bonding.[4] Another example is the trends in reactivity, such as boron's tendency to form reactive compounds with hydrogen.[5]

Chemical reactivity

Hydrides

Most of the elements in the boron group show increasing reactivity as the elements get heavier in atomic mass and higher in atomic number. Boron, the first element in the group, is generally unreactive with many elements except under high temperatures, although it is capable of forming quite a few compounds with hydrogen, and are sometimes called boranes.[6] The simplest borane is diborane, or B2H6.[5] Another example is B10H14.

The next group 13 elements, aluminum and gallium, form fewer stable hydrides, but AlH3 and GaH3 are known.[7] Indium, the next element in the group, is not known to form many hydrides, except in complex compounds such as H3InP(Cy)3, which is considered to be a phosphine.[8] As for thallium, though, no stable compound with hydrogen has been synthesized in any laboratory.

Oxides

All of the boron group elements are known to form a trivalent oxide with two atoms of the element bonded covalently with three atoms of oxygen. These elements show a trend in the pH by it being from a higher to lower pH (from acidic to basic).[14] Boron oxide (B2O3) is shown to be slightly acidic, aluminum and gallium oxide (Al2O3 and Ga2O3, respectively) are amphoteric, indium(III) oxide [15] (In2O3) is nearly amphoteric, and thallium(III) oxide (Tl2O3) is a Lewis base, because it dissolves with acids to form salts.[16] Each of these are stable compounds, but thallium oxide is shown to decompose at temperatures higher than 100°C.

B2O3 powder

Halides

The elements in group thirteen are also capable of forming stable halides with the halogens. All of the members in the boron group usually form a compound with the formula MX3 (M is a boron group element and X is a halogen.) The only exception to this is thallium(III) iodide.[17] Fluorine, the first halogen, is able to form stable compounds with every element in which it has been attempted,[18][note 2] and the boron group is no exception. It is even hypothesized that ununtrium could form a compound with fluorine, UutF3, before spontaneously decaying due to ununtrium's radioactivity. Chlorine also forms stable compounds with all of the elements in the boron group, including thallium and also hypothetically reacting with element 113. Like the other halogens, all of the elements will react with Bromine under the right conditions, but less vigorously than both chlorine and fluorine. Iodine will react with all natural elements in the periodic table except for the noble gases, and is notable for its explosive reaction with aluminum to form 2AlI3.[19] Astatine, the heaviest halogen, has only formed a few compounds due to its radioactvity and short half-life and no reports of a compound with an At-B,Al,Ga,In,Tl,Uut bond have been seen, although scientists think that it should form salts with metals.[20]

Physical properties

It has been noticed that the elements in the boron group have similar physical properties. It has also been noticed that boron is an exception to most of the physical properties of the group 13 elements. For example, all of the elements in the boron group except boron itself are soft in appearance. Boron tends to be hard. In addition to that, all of the elements in group 13 are pretty reactive at moderate temperatures except boron, which is only pretty reactive at very high temperatures. One characteristic that all do have in common is that all have three electrons in their valence shells. Boron, being a metalloid, is an insulator at room temperature, but a good conductor at high temperatures.[21] Unlike boron, the metals in the group are good conductors at usual conditions.[22][23] The exact same can go for electricity because boron is not good at conducting electricity at cool temperatures but is good at high temperatures, and the other metals conduct it. This is in accordance with the long standing generalization that all metals conduct heat and electricity better than most non-metals.[24]

Oxidation States

In the group 13 elements, the inert s-pair effect acts on them, especially the heavier elements such as thallium. This results in a variety of oxidation states. In the lighter elements, the +3 state is the most stable, but as you move down the group, the +1 state becomes more pronounced and becomes the most stable for thallium.[25] Boron is capable of forming compounds with other oxidization states lower than three such as one or two. Aluminum can do the same.[26] Gallium cannot form compounds with the oxidation state +2 but can with +1 and +3. Indium is also like gallium but the +1 compounds are more stable than the other elements. Thallium has the maximum strength of the inert pair effect and shows a stable oxidation state +1 but not +3, although the +3 state is seen in some compounds.

Isotopes

With the exception of the synthetic ununtrium, all of the elements of the boron group have stable isotopes. But, due to the fact that all of their atomic numbers are odd, boron, gallium and thallium have only two stable isotopes, and aluminum and indium only have one, making the two last elements monoisotopic. 10B and 11B are both stable, as are 27Al, 69Ga and 71Ga, 113In, and 203Tl and 205Tl.[27] In addition, all of the isotopes stated above are found in nature in macroscopic quantities at any time. This group is special with its isotopes because it contains some of the heaviest stable isotopes ever found. Only lead has a heavier stable isotope. In theory, though, all elements with an isotope above atomic mass > 40 is supposed to be unstable to decays such as spontaneous fission and alpha decay. Also in theory, all elements with an isotope below atomic mass > 40 is supposed to be energetically stable to all forms of decay except proton decay which has not yet been observed ever.

Like all other elements, the group 13 elements have radioactive isotopes that have either been found in trace quantities in nature, or have been produced synthetically. The longest-lived unstable isotope out of all of them is indium's isotope 115In with an extremely long half-life of 4.41 × 1014 y. This isotope is a relatively important isotope in indium's radioisotopes. The shortest stable isotope, however, is extremely short, being boron's isotope with the least neutrons and a half-life long enough to measure. it is 7B and its half-life is a mere 350±50 x 10−24 s. Some radioisotopes have important roles in scientific research and a few even can be used in the production of goods or, more rarely, for commercial uses in goods itself.[28]

History

The boron group has had many names over the past years. In the old naming system of the groups, it was dubbed 'group IIIB' in the European naming system and 'group IIIA' in the old American naming system. This group has also gained two collective names, the earth metals and the triels. The later name stemmed from the characteristic that all of these elements without exception have three valence electrons in their valence shells.[29]

Boron was known to the ancient Egyptians, but only in the mineral borax. The real metalloid was not known in its pure form until a thousand years later, when Humphry Davy was able to extract it by the method of electrolysis. In 1808, Davy devised an experiment in which he dissolved a boron-containing compound in water and then sent an electric current through it, causing the elements of the compound to transform back into their pure state. He shifted from electrolysis to reduction with sodium to produce larger quantities. Davy named the element boracium. At the same time two French chemists, Joseph Louis Gay-Lussac and Louis Jacques Thénard used iron to reduce boric acid. They were able to oxidize the produced boron with oxygen to boron oxide.[30][31]

Aluminum, like boron, was first known in minerals before it was finally extracted from it. It was known in the mineral alum, a common mineral in some areas of the world. On its way to being extracted, both Lavoiser and Davy had each separately tried to extract it, but to no avail. Humphry Davy, though, had given the metal the still widely used name aluminum. It was only that in 1825 that the Danish scientist Hans Christian Ørsted successfully prepared a rather impure form of the element. But with the discovery came many improvements as to how to extract the element, and a significant one was developed just two years later by Friedrich Wöhler who modified slightly the procedure with a better result, though still impure. The first pure sample of aluminum was credited to Henri Etienne Sainte-Claire Deville, who used sodium instead of potassium. At that time aluminum was regarded as a precious metal and was displayed next to other real precious metals such as gold and silver.[31][32] The method to electrolysis aluminum oxide dissolved in cryolite by Charles Martin Hall and Paul Héroult still used today was developed in the late 1880s[31]

Zinc blende, more commonly known as sphalerite

Thallium, the last and heaviest stable element in the boron group, was discovered by William Crookes and Claude-Auguste Lamy in 1861 in a similar way to indium. Unlike the other chemical elements gallium and indium, thallium was not predicted by Dmitri Mendeleev. As a result, no one was really looking for it until the 1850s when Crookes and Lamy were examining residues of the sulfuric acid production. While examining the spectroscopic lines both saw a completely different spectrical line. It was a streak of deep green. Thus Crookes named it after the Greek word θαλλός (thallos), which signifies the word green shoot or twig. Lamy was able to produce larger amounts of the new metal and determined most of the chemical and physical properties of thallium[33][34]

Indium is the fourth element of the boron group and yet was discovered before the third, gallium, and after the fifth, thallium. It was discovered while two chemists, Ferdinand Reich and his assistant, Hieronymous Theodor Richter, in 1863, were looking for the spectroscopic lines of the newly discovered element, thallium, in a sample of the mineral zinc-blende, also known as sphalerite (ZnS). First, Reich had heated it in a coil of platinum metal and observed through a spectroscope the spectroscopic lines that appeared after it was thoroughly heated. While looking for the expectant green streak in its lines, an unexpected spectrum appeared. Instead of the green lines that were supposed to be seen in thallium, he saw a new, deep indigo blue line in it. He was astonished and deduced that it must be a new element. They decided to name it indium, after the characteristic indigo line.[33][35]

Gallium minerals were not known before gallium was discovered in August 1875. It was one of the elements that the inventor of the periodic table, Dimitri Mendeleev, had predicted to exist six years earlier. It was discovered by French Paul Emile Lecoq de Boisbaudran, while examining the spectroscopic lines in the ore zinc blende (ZnS), he found new spectroscopic lines that indicated that a new element was in the ore. In just three months, he had been able to obtain a sample of this newly found element. Paul was even able to purify the element by dissolving it in a potassium hydroxide (KOH) solution and then sending an electric current through it. The next month, he presented his findings at the French Academy of Sciences. He then named it "gallium" after the Greek name for France.[36][37]

It can be argued that the last confirmed element in the boron group, ununtrium, was not really "discovered", but "created" or synthesized. Nonetheless, though, the element's synthesis is credited as a collaboration to both the Dubna Joint Institute for Nuclear Research team in Russia, and the Lawrence Livermore National Laboratory in the United States, but it was the Dubna team who successfully conducted the experiment. It was discovered in the decay chain of element 115, or ununpentium, when the scientists had successfully detected a few precious atoms of ununtrium, or eka-thallium. It was discovered in August 2003 although the results were published in January of the following year. Since then, around 13 atoms have been synthesized to date with various isotopes being characterized.[38]

Etymology

The word boron comes from the Arabic word for the mineral borax,(بورق, boraq) which was known before boron was ever extracted. The '-on' part of boron was thought to be taken from carbon. In other words, it's etymology can be regarded as a combination of borax and carbon.[39] Aluminum was named by Humphry Davy in the early 1800's. It is derived from the Greek word alumen, meaning bitter salt. The '-ium' was added to signify that it is an element.[40][41] Gallium is derived from the Latin word gallia, meaning France, the place of discovery for gallium.[42] Indium comes from the Latin word indicum, meaning indigo and referring to the prominent indigo spectroscopic line found in indium.[43] Thallium, like indium, is named after the Greek word for its spectroscopic line's color. In this case, it is green, thus it is given the name thallos, which signifies the words green twig or green shoot.[44][45] Ununtrium is currently a temporary name assigned by the IUPAC to it until its discovery is confirmed.[46] (see IUPAC nomenclature).

Occurance and abundance

Boron

Boron is a very light element with an atomic number of 5, and it is an element that is almost never found as an free element in nature. In fact, it is very low in abundance, with only 0.001% (10 ppm)[47] in the Earth's crust at any time. Although it is not usually found in the Earth's crust, it is known to be found in over a hundred different minerals and ores. The main source is in borax, but it is also found combined in colemanite, boracite, kernite, tusionite, berborite and fluoborite.[48] Major world miners and extractors of boron include the United States, Turkey, Argentina, China, Bolivia and Peru. By far Turkey is the most prominent of all of these, accounting for around 70% of all boron extraction in the world. The United States comes in second with most of its yield coming from the state California.[49]

Aluminum

Aluminum, unlike boron, is the most abundant metal in the Earth's crust, and the third most abundant element. It composes about 8.2% (82,000 ppm) of the Earth, third only to oxygen and silicon.[47] It is like boron, however, in the fact that it is uncommon in nature as a free element. This is due to aluminum’s tendency to attract oxygen atoms and forms several aluminum oxides. Aluminum is now known to be in nearly as many minerals as boron, such as garnets, turquoises and beryls, but the main extraction source lies in the ore bauxite. The countries Ghana, Surinam, Russia and Indonesia are the world's leaders in the extraction of aluminum. Other major countries include Australia, Guinea and Brazil.[50]

Gallium

Gallium is a relatively rare element in the Earth's crust and is not found in many minerals like its lighter homologues in the group. Also unlike aluminum and boron, its abundance on the Earth is a mere 0.0018% (18 ppm).[47] Its abundance and production is very low compared to other elements, but has increased greatly over the years since its discovery with some advances of the methods for extracting gallium. Gallium can be found as a trace in a variety of ores and minerals. These include the ore bauxite and the minerals diaspore and germanite. A precious few minerals have been found which include a larger content of gallium such as gallite. Unfortunately, minerals such as gallite are too rare to be counted as a major source and are negligible. Sometimes, trace amounts of gallium have been found in coal too.[51]

Indium

Indium, is also a rare element in the boron group, to the extent that it is even less abundant than gallium. Its estimation to its abundance is only 0.00005% (0.05 ppm).[47] The like most other elements found in ores and minerals, the extraction process of the element is becoming more efficient in recent years, ultimately leading to a larger yield. Indium is currently found to be the 61st element in the earth's crust. As a result, though, an extremely small number of indium minerals are known, and each with a rare abundance in the earth. One example is indite. Indium is also known to be found in several zinc ores, but only in minute quantities. The same can also go for its abundance it copper and lead ores. Canada is the world's leader in the production of the element, but both the United States and China produce a comparable amount of indium.[52]

Thallium

Bundle of fiberglass

Thallium is neither rare nor common in the Earth's crust; it is somewhere in the middle. Its estimated to be at 0.0006% (0.6 ppm).[47] It is found on the ground in some rocks, in the soil and in clay. Also it is found in many sulfide ores such as ones with iron, zinc and cobalt. In minerals it is found in a moderate amount. Some examples are Crookesite, the mineral that owes to its discovery, lorandite, routhierite, bukovite, hutchinsonite and sabatierite. Other minerals with smaller amounts of thallium are very rare and cannot and do not serve as a primary source of thallium. Thallium is the 56th element in the earth's crust, and thus is more abundant than indium by a sizeable difference. Macedonia is considered as a notable thallium extractor and producer.

Ununtrium

Ununtrium is an element that is never found in nature but is synthesized in a laboratory. Therefore, it is a synthetic element with no stable isotopes.

Applications

With the exception of synthetic ununtrium, each and every element in the boron group has numerous applications and uses in the production and the content of many items.

Boron has been known to have many industrial applications since decades ago, and new applications are still being found for it. A common application is the usage in fiberglass.[53] As an alternative to fiberglass, though, boron has had a rapidly expanding place in borosilicate glass, a different type of glass with its own advantages and disadvantages, the most notable one being its resistance to thermal expansion much more than regular glass. Another commercially expanding use of boron and its derivatives are its use in ceramics and other decorations. Due to the many pros and unique properties of several of boron's compounds, especially oxides, it is replacing other less useful materials and elements with itself. Its uses include in pots, vases, plates, and ceramic handles on pans, because it does not conduct electricity very well (it is an insulator). The compound borax is used in clothes bleach and tooth bleach. As stated above, boron and some of its compounds are very hard. This opens a wide window of uses for the element. A small part (5%) is used for agricultural uses. Finally, some minor applications are in use for boron and its compounds.[54]

Aluminum is a metal which we almost always use in our everyday lives. It is used every day for many uses; the most often used is in construction, in electricity, especially as the conductor in cables and for cooking and preserving food. Because aluminum does not have any effect in mere contact with food, it is used in canning food products such as fish, produce, crops and most other food. It's high affinity for the element oxygen not only makes aluminum oxides readily found in the crust, but makes it a powerful reducing agent. And, when pure aluminum is ground into a fine powder and put in air, usually in places where oxygen is rich in the air, it rapidly combines with the oxygen back into an oxide generating a huge amount of heat in the process (about 5500 °F or 3037 °C). Therefore, it can be used for welding and other applications where a large amount of heat is needed. Aluminum is also used in alloys for making lightweight bodies for airplanes and helicopters. Cars also sometimes incorporate aluminum in their framework and body. It can be and is used in defense equipment. As a less widespread application, it is used as a component in decorations and sometimes in guitars. The element is also in use in a diverse range of electronics.[55][56]

In the past, gallium and its derivatives rarely was useful. It wasn't until the past decades that gallium has found more applications. Gallium arsenide has been used in semiconductors, in amplifiers, in solar cells (for example in satellites) and in tunnel diodes for FM transmitter circuits. Gallium alloys are used mostly for dental purposes. gallium-ammonium chloride is used for leads in transistors.[57] A major use of gallium is its use in LED lights. Pure gallium has been used as dopants in semiconductors.[58] Gallium has the property of being able to 'wet' glass and porcelain, and thus can be used

Gallium in blue LED's

to make mirrors and very reflective objects. Also, gallium can be alloyed with other metals to give the resulting alloy a low melting point. This element can additionally be used in electronic devices with other elements.

Indium is the fourth element in the group 13 elements and is also used, like the other elements. Its uses can be divided into four parts: the largest part (70%) is used for coatings of some materials, usually combined as indium tin oxide (ITO) another part (12%) is used in alloys and solders, another 12% for its usage in electrical components and in semiconductors, and a final 6% for other, more minor, applications.[59] Indium is used for many things, including platings, bearings, display devices, heat reflection objects, phosphors, nuclear rods, amongst other minor applications. Over the years, the specific compound indium tin oxide has found its way into a wide number of applications like in glass coatings, solar collectors, streetlights, electrophosetic displays (EPD's), electroluminescent displays (ELD's), plasma display panels (PDP's), electrochemic displays (EC's), field emission displays (FED's), sodium lamps, windshield glass and cathode ray tubes. These wide range of applications for indium tin oxide is accredited for almost three quarters of the world consumption, and thus is the main use for indium.[60]

Thallium has much more uses as a lone element when compared to the other boron group elements. By itself, thallium is used in low-melting glasses, photoelectric cells, switches, mercury alloys for low-range glass thermometers and thallium salts. It can also be used in lamps and electronics. The element is used in myocardial imaging, too. Thallium has been the topic of some researches for its possible use with semiconductors and it is a known catalyst in organic synthesis. Thallium hydroxide (TlOH) is used mainly in the production of other thallium compounds. Thallium sulfate (Tl2SO4) is known to be an outstanding vermin killer. Therefore, it is a main component in some rat and mice poisons. However, the United States and some countries in Europe have banned the substance because of its elevated toxicity to humans. In other countries, though, buying goods with the substance is readily increasing. Tl2SO4 is also used in optical systems.[61]

Biological role

None of the group 13 elements have a major biological role in complex animals, but more than one element is at least associated with a living being. Like other groups, the lighter elements usually have more biological roles than the heavier elements if they have any. The other, heavier, elements are toxic as are the other associated elements in their periods. Boron was found to be a trace element in humans, and it is essential in most plants, because it is of use for many functions of the cells, such as the strengthening of the cell wall. There is still an ongoing debate to whether boron is more than just a trace element. Boron's chemistry does allow it to form complexes with important molecules such as carbohydrates, so it is very probable that it could be of greater use in the human body than previously thought. Boron has also been shown to be able to replace iron in some of its functions, particularly wound healing.[62] Aluminum has no known biological role in plants or animals. Gallium is not essential for the human body, but its relation to iron(III) allows it to be able to bind itself to iron transport proteins and storage proteins.[63] Gallium can also stimulate metabolism. Due to the fact that indium and its heavier homologues have a high atomic number, they have no biological role, although indium salts in small doses can stimulate metabolism like gallium.[35]

The skull and crossbones sign is put on items containing thallium

Toxicity

All of the elements in the boron group, when given a high enough dose, can be toxic, although some are only toxic for plants, some only for animals, and some for both.

Boron to Gallium

Boron, for example, was measured to be toxic in barley in concentrations exceeding 20 mM.[64] Unfortunately, in plants, the symptoms of boron toxicity are numerous, including reduced cell division, decreased shoot and root growth, decrease in production of leaf chlorophyll, inhabitation of photosynthesis, lower stomata conductance, reduced proton extrusion from roots and deposition of lignin and suborgin, among some others.[65] Aluminum does not present a promenent toxicity hazard when in small quantities. It is only when it is in very large quantities that it is slightly toxic. Gallium is not considered toxic, although there could be some possible side effects.

Indium and Thallium

Indium is not toxic and it is handled with nearly the same precautions as gallium, although some of its compounds are toxic, with a toxicity ranging from relatively low to moderate. Thallium, unlike gallium and indium, is extremely toxic, and has caused the death by poisoning of many people. Its most noticeable side effect when even a tiny quantity is administered is hair loss all over the body, but it causes a wide range of other ones. This is because it will disrupt the growth of hair and other organs, and will therefore make it stop growing. Its nearly clear color, its odorless nature and tasteless compounds have been used for a long time as a murderer's weapon. The cases skyrocketed when thallium and its also toxic compound thallium sulfate was introduced as a poison for rats and other insects. As a result, thallium used as a poison has been prohibited in many countries, including the USA since 1975. Ununtrium is a highly unstable element and decays by emitting radioactive particles. It is, without a doubt, extremely toxic.[66]

Notes

  1. ^ To this date, no ununtrium compounds have been synthesized, and all proposed compounds are entirely theoretical.
  2. ^ Except neon and helium, the two noble gases which no stable compound has been formed.

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