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1 3 3 5 5 7 7 octaethyl s hydrindacen 4 yl germanium is able to form a double bond with oxygen germanone germanium hydride and germanium tetrahydride are very flammable and even explosive when mixed with air 49 isotopes edit main article isotopes of germanium germanium occurs in 5 natural isotopes 70 ge 72 ge 73 ge 74 ge and 76 ge of these 76 ge is very slightly radioactive decaying by double beta decay with a half life of 1 78 10 21 years 74 ge is the most common isotope having a natural abundance of approximately 36 76 ge is the least common with a natural abundance of approximately 7 50 when bombarded with alpha particles the isotope 72 ge will generate stable 77 se releasing high energy electrons in the process 51 because of this it is used in combination with radon for nuclear batteries 51 at least 27 radioisotopes have also been synthesized ranging in atomic mass from 58 to 89 the most stable of these is 68 ge decaying by electron capture with a half life of 270 95 d ays the least stable is 60 ge with a half life of 30 ms while most of germanium s radioisotopes decay by beta decay 61 ge and 64 ge decay by β delayed proton emission 50 84 ge through 87 ge isotopes also exhibit minor β delayed neutron emission decay paths 50 occurrence edit see also category germanium minerals renierite germanium is created by stellar nucleosynthesis mostly by the s process in asymptotic giant branch stars the s process is a slow neutron capture of lighter elements inside pulsating red giant stars 52 germanium has been detected in some of the most distant stars 53 and in the atmosphere of jupiter 54 germanium s abundance in the earth s crust is approximately 1 6 ppm 55 only a few minerals like argyrodite briartite germanite renierite and sphalerite contain appreciable amounts of germanium 27 56 only few of them especially germanite are very rarely found in mineable amounts 57 58 59 some zinc copper lead ore bodies contain enough germanium to justify extraction from the final ore concentrate 55 an unusual natural enrichment process causes a high content of germanium in some coal seams discovered by victor moritz goldschmidt during a broad survey for germanium deposits 60 61 the highest concentration ever found was in hartley coal ash with as much as 1 6 germanium 60 61 the coal deposits near xilinhaote inner mongolia contain an estimated 1600 tonnes of germanium 55 production edit about 118 tonnes of germanium were produced in 2011 worldwide mostly in china 80 t russia 5 t and united states 3 t 27 germanium is recovered as a by product from sphalerite zinc ores where it is concentrated in amounts as great as 0 3 62 especially from low temperature sediment hosted massive zn pb cu ba deposits and carbonate hosted zn pb deposits 63 a recent study found that at least 10 000 t of extractable germanium is contained in known zinc reserves particularly those hosted by mississippi valley type deposits while at least 112 000 t will be found in coal reserves 64 65 in 2007 35 of the demand was met by recycled germanium 55 year cost kg 66 1999 1 400 2000 1 250 2001 890 2002 620 2003 380 2004 600 2005 660 2006 880 2007 1 240 2008 1 490 2009 950 2010 940 2011 1 625 2012 1 680 2013 1 875 2014 1 900 2015 1 760 2016 950 2017 1 358 2018 1 300 2019 1 240 2020 1 000 while it is produced mainly from sphalerite it is also found in silver lead and copper ores another source of germanium is fly ash of power plants fueled from coal deposits that contain germanium russia and china used this as a source for germanium 67 russia s deposits are located in the far east of sakhalin island and northeast of vladivostok the deposits in china are located mainly in the lignite mines near lincang yunnan coal is also mined near xilinhaote inner mongolia 55 the ore concentrates are mostly sulfidic they are converted to the oxides by heating under air in a process known as roasting ges 2 3 o 2 geo 2 2 so 2 some of the germanium is left in the dust produced while the rest is converted to germanates which are then leached together with zinc from the cinder by sulfuric acid after neutralization only the zinc stays in solution while germanium and other metals precipitate after removing some of the zinc in the precipitate by the waelz process the residing waelz oxide is leached a second time the dioxide is obtained as precipitate and converted with chlorine gas or hydrochloric acid to germanium tetrachloride which has a low boiling point and can be isolated by distillation 67 geo 2 4 hcl gecl 4 2 h 2 o geo 2 2 cl 2 gecl 4 o 2 germanium tetrachloride is either hydrolyzed to the oxide geo 2 or purified by fractional distillation and then hydrolyzed 67 the highly pure geo 2 is now suitable for the production of germanium glass it is reduced to the element by reacting it with hydrogen producing germanium suitable for infrared optics and semiconductor production geo 2 2 h 2 ge 2 h 2 o the germanium for steel production and other industrial processes is normally reduced using carbon 68 geo 2 c ge co 2 applications edit the major end uses for germanium in 2007 worldwide were estimated to be 35 for fiber optics 30 infrared optics 15 polymerization catalysts and 15 electronics and solar electric applications 27 the remaining 5 went into such uses as phosphors metallurgy and chemotherapy 27 optics edit a typical single mode optical fiber germanium oxide is a dopant of the core silica item 1 core 8 µm cladding 125 µm buffer 250 µm jacket 400 µm the notable properties of germania geo 2 are its high index of refraction and its low optical dispersion these make it especially useful for wide angle camera lenses microscopy and the core part of optical fibers 69 70 it has replaced titania as the dopant for silica fiber eliminating the subsequent heat treatment that made the fibers brittle 71 at the end of 2002 the fiber optics industry consumed 60 of the annual germanium use in the united states but this is less than 10 of worldwide consumption 70 gesbte is a phase change material used for its optic properties such as that used in rewritable dvds 72 because germanium is transparent in the infrared wavelengths it is an important infrared optical material that can be readily cut and polished into lenses and windows it is especially used as the front optic in thermal imaging cameras working in the 8 to 14 micron range for passive thermal imaging and for hot spot detection in military mobile night vision and fire fighting applications 68 it is used in infrared spectroscopes and other optical equipment that require extremely sensitive infrared detectors 70 it has a very high refractive index 4 0 and must be coated with anti reflection agents particularly a very hard special antireflection coating of diamond like carbon dlc refractive index 2 0 is a good match and produces a diamond hard surface that can withstand much environmental abuse 73 74 electronics edit germanium can be alloyed with silicon and silicon germanium alloys are rapidly becoming an important semiconductor material for high speed integrated circuits circuits utilizing the properties of si sige heterojunctions can be much faster than those using silicon alone 75 silicon germanium is beginning to replace gallium arsenide gaas in wireless communications devices 27 the sige chips with high speed properties can be made with low cost well established production techniques of the silicon chip industry 27 high efficiency solar panels are a major use of germanium because germanium and gallium arsenide have nearly identical lattice constant germanium substrates can be used to make gallium arsenide solar cells 76 germanium is the substrate of the wafers for high efficiency multijunction photovoltaic cells for space applications such as the mars exploration rovers which use triple junction gallium arsenide on germanium cells 77 high brightness leds used for automobile headlights and to backlight lcd screens are also an important application 27 germanium on insulator geoi substrates are seen as a potential replacement for silicon on miniaturized chips 27 cmos circuit based on geoi substrates has been reported recently 78 other uses in electronics include phosphors in fluorescent lamps 32 and solid state light emitting diodes leds 27 germanium transistors are still used in some effects pedals by musicians who wish to reproduce the distinctive tonal character of the fuzz tone from the early rock and roll era most notably the dallas arbiter fuzz face 79 other uses edit a pet bottle germanium dioxide is also used in catalysts for polymerization in the production of polyethylene terephthalate pet 80 the high brilliance of this polyester is especially favored for pet bottles marketed in japan 80 in the united states germanium is not used for polymerization catalysts 27 due to the similarity between silica sio 2 and germanium dioxide geo 2 the silica stationary phase in some gas chromatography columns can be replaced by geo 2 81 in recent years germanium has seen increasing use in precious metal alloys in sterling silver alloys for instance it reduces firescale increases tarnish resistance and improves precipitation hardening a tarnish proof silver alloy trademarked argentium contains 1 2 germanium 27 semiconductor detectors made of single crystal high purity germanium can precisely identify radiation sources for example in airport security 82 germanium is useful for monochromators for beamlines used in single crystal neutron scattering and synchrotron x ray diffraction the reflectivity has advantages over silicon in neutron and high energy x ray applications 83 crystals of high purity germanium are used in detectors for gamma spectroscopy and the search for dark matter 84 germanium crystals are also used in x ray spectrometers for the determination of phosphorus chlorine and sulfur 85 germanium is emerging as an important material for spintronics and spin based quantum computing applications in 2010 researchers demonstrated room temperature spin transport 86 and more recently donor electron spins in germanium has been shown to have very long coherence times 87 germanium and health edit germanium is not considered essential to the health of plants or animals 88 germanium in the environment has little or no health impact this is primarily because it usually occurs only as a trace element in ores and carbonaceous materials and the various industrial and electronic applications involve very small quantities that are not likely to be ingested 27 for similar reasons end use germanium has little impact on the environment as a biohazard some reactive intermediate compounds of germanium are poisonous see precautions below 89 germanium supplements made from both organic and inorganic germanium have been marketed as an alternative medicine capable of treating leukemia and lung cancer 24 there is however no medical evidence of benefit some evidence suggests that such supplements are actively harmful 88 u s food and drug administration research has concluded that inorganic germanium when used as a nutritional supplement presents potential human health hazard 48 some germanium compounds have been administered by alternative medical practitioners as non fda allowed injectable solutions soluble inorganic forms of germanium used at first notably the citrate lactate salt resulted in some cases of renal dysfunction hepatic steatosis and peripheral neuropathy in individuals using them over a long term plasma and urine germanium concentrations in these individuals several of whom died were several orders of magnitude greater than endogenous levels a more recent organic form beta carboxyethylgermanium sesquioxide propagermanium has not exhibited the same spectrum of toxic effects 90 certain compounds of germanium have low toxicity to mammals but have toxic effects against certain bacteria 29 precautions for chemically reactive germanium compounds edit while use of germanium itself does not require precautions some of germanium s artificially produced compounds are quite reactive and present an immediate hazard to human health on exposure for example germanium chloride and germane geh 4 are a liquid and gas respectively that can be very irritating to the eyes skin lungs and throat 91 see also edit germanene vitrain history of the transistor notes edit from greek argyrodite means silver containing 8 just as the existence of the new element had been predicted the existence of the planet neptune had been predicted in about 1843 by the two mathematicians john couch adams and urbain le verrier using the calculation methods of celestial mechanics they did this in attempts to explain the fact that the planet uranus upon very close observation appeared to be being pulled slightly out of position in the sky 11 james challis started searching for it in july 1846 and he sighted this planet on september 23 1846 12 r hermann published claims in 1877 of his discovery of a new element beneath tantalum in the periodic table which he named neptunium after the greek god of the oceans and seas 13 14 however this metal was later recognized to be an alloy of the elements niobium and tantalum 15 the name neptunium was later given to the synthetic element one step past uranium in the periodic table which was discovered by nuclear physics researchers in 1940 16 references edit standard atomic weights germanium ciaaw 2009 new type of zero valent tin compound chemistry europe 27 august 2016 magnetic susceptibility of the elements and inorganic compounds in handbook of chemistry and physics 81st edition crc press weast robert 1984 crc handbook of chemistry and physics boca raton florida chemical rubber company publishing pp e110 isbn 0 8493 0464 4 a b c d properties of germanium ioffe institute avarmaa katri klemettinen lassi o brien hugh taskinen pekka jokilaakso ari june 2019 critical metals ga ge and in experimental evidence for smelter recovery improvements minerals 9 6 367 bibcode 2019mine 9 367a doi 10 3390 min9060367 kaji masanori 2002 d i mendeleev s concept of chemical elements and the principles of chemistry pdf bulletin for the history of chemistry 27 1 4 16 archived from the original pdf on 2008 12 17 retrieved 2008 08 20 argyrodite ag 8 ges 6 pdf report mineral data publishing archived pdf from the original on 2016 03 03 retrieved 2008 09 01 a b c d e winkler clemens 1887 mittheilungen über des germanium zweite abhandlung j prak chemie in german 36 1 177 209 doi 10 1002 prac 18870360119 archived from the original on 2012 11 03 retrieved 2008 08 20 a b c d winkler clemens 1887 germanium ge a new nonmetal element berichte der deutschen chemischen gesellschaft in german 19 1 210 211 doi 10 1002 cber 18860190156 archived from the original on december 7 2008 adams j c november 13 1846 explanation of the observed irregularities in the motion of uranus on the hypothesis of disturbance by a more distant planet monthly notices of the royal astronomical society 7 9 149 152 bibcode 1846mnras ...
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