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halerite the primary ore of zinc though germanium is also recovered commercially from silver lead and copper ores elemental germanium is used as a semiconductor in transistors and various other electronic devices historically the first decade of semiconductor electronics was based entirely on germanium presently the major end uses are fibre optic systems infrared optics solar cell applications and light emitting diodes leds germanium compounds are also used for polymerization catalysts and have most recently found use in the production of nanowires this element forms a large number of organogermanium compounds such as tetraethylgermanium useful in organometallic chemistry germanium is considered a technology critical element 6 germanium is not thought to be an essential element for any living organism some complex organic germanium compounds are being investigated as possible pharmaceuticals though none have yet proven successful similar to silicon and aluminium naturally occurring germanium compounds tend to be insoluble in water and thus have little oral toxicity however synthetic soluble germanium salts are nephrotoxic and synthetic chemically reactive germanium compounds with halogens and hydrogen are irritants and toxins contents 1 history 2 characteristics 2 1 chemistry 2 2 isotopes 2 3 occurrence 3 production 4 applications 4 1 optics 4 2 electronics 4 3 other uses 5 germanium and health 5 1 precautions for chemically reactive germanium compounds 6 see also 7 notes 8 references 9 external links history edit prediction of germanium 70 periodic table 1869 in his report on the periodic law of the chemical elements in 1869 the russian chemist dmitri mendeleev predicted the existence of several unknown chemical elements including one that would fill a gap in the carbon family located between silicon and tin 7 because of its position in his periodic table mendeleev called it ekasilicon es and he estimated its atomic weight to be 70 later 72 in mid 1885 at a mine near freiberg saxony a new mineral was discovered and named argyrodite because of its high silver content note 1 the chemist clemens winkler analyzed this new mineral which proved to be a combination of silver sulfur and a new element winkler was able to isolate the new element in 1886 and found it similar to antimony he initially considered the new element to be eka antimony but was soon convinced that it was instead eka silicon 9 10 before winkler published his results on the new element he decided that he would name his element neptunium since the recent discovery of planet neptune in 1846 had similarly been preceded by mathematical predictions of its existence note 2 however the name neptunium had already been given to another proposed chemical element though not the element that today bears the name neptunium which was discovered in 1940 note 3 so instead winkler named the new element germanium from the latin word germania for germany in honor of his homeland 10 argyrodite proved empirically to be ag 8 ges 6 because this new element showed some similarities with the elements arsenic and antimony its proper place in the periodic table was under consideration but its similarities with dmitri mendeleev s predicted element ekasilicon confirmed that place on the periodic table 10 17 with further material from 500 kg of ore from the mines in saxony winkler confirmed the chemical properties of the new element in 1887 9 10 18 he also determined an atomic weight of 72 32 by analyzing pure germanium tetrachloride gecl 4 while lecoq de boisbaudran deduced 72 3 by a comparison of the lines in the spark spectrum of the element 19 winkler was able to prepare several new compounds of germanium including fluorides chlorides sulfides dioxide and tetraethylgermane ge c 2 h 5 4 the first organogermane 9 the physical data from those compounds which corresponded well with mendeleev s predictions made the discovery an important confirmation of mendeleev s idea of element periodicity here is a comparison between the prediction and winkler s data 9 property ekasilicon mendeleev prediction 1871 germanium winkler discovery 1887 atomic mass 72 64 72 63 density g cm 3 5 5 5 35 melting point c high 947 color gray gray oxide type refractory dioxide refractory dioxide oxide density g cm 3 4 7 4 7 oxide activity feebly basic feebly basic chloride boiling point c under 100 86 gecl 4 chloride density g cm 3 1 9 1 9 until the late 1930s germanium was thought to be a poorly conducting metal 20 germanium did not become economically significant until after 1945 when its properties as an electronic semiconductor were recognized during world war ii small amounts of germanium were used in some special electronic devices mostly diodes 21 22 the first major use was the point contact schottky diodes for radar pulse detection during the war 20 the first silicon germanium alloys were obtained in 1955 23 before 1945 only a few hundred kilograms of germanium were produced in smelters each year but by the end of the 1950s the annual worldwide production had reached 40 metric tons 44 short tons 24 the development of the germanium transistor in 1948 25 opened the door to countless applications of solid state electronics 26 from 1950 through the early 1970s this area provided an increasing market for germanium but then high purity silicon began replacing germanium in transistors diodes and rectifiers 27 for example the company that became fairchild semiconductor was founded in 1957 with the express purpose of producing silicon transistors silicon has superior electrical properties but it requires much greater purity that could not be commercially achieved in the early years of semiconductor electronics 28 meanwhile the demand for germanium for fiber optic communication networks infrared night vision systems and polymerization catalysts increased dramatically 24 these end uses represented 85 of worldwide germanium consumption in 2000 27 the us government even designated germanium as a strategic and critical material calling for a 146 ton 132 tonne supply in the national defense stockpile in 1987 24 germanium differs from silicon in that the supply is limited by the availability of exploitable sources while the supply of silicon is limited only by production capacity since silicon comes from ordinary sand and quartz while silicon could be bought in 1998 for less than 10 per kg 24 the price of germanium was almost 800 per kg 24 characteristics edit under standard conditions germanium is a brittle silvery white semi metallic element 29 this form constitutes an allotrope known as α germanium which has a metallic luster and a diamond cubic crystal structure the same as diamond 27 while in crystal form germanium has a displacement threshold energy of 19 7 0 5 0 6 ev displaystyle 19 7_ 0 5 0 6 text ev 30 at pressures above 120 kbar germanium becomes the allotrope β germanium with the same structure as β tin 31 like silicon gallium bismuth antimony and water germanium is one of the few substances that expands as it solidifies i e freezes from the molten state 31 germanium is a semiconductor zone refining techniques have led to the production of crystalline germanium for semiconductors that has an impurity of only one part in 10 10 32 making it one of the purest materials ever obtained 33 the first metallic material discovered in 2005 to become a superconductor in the presence of an extremely strong electromagnetic field was an alloy of germanium uranium and rhodium 34 pure germanium is known to spontaneously extrude very long screw dislocations referred to as germanium whiskers the growth of these whiskers is one of the primary reasons for the failure of older diodes and transistors made from germanium as depending on what they eventually touch they may lead to an electrical short 35 chemistry edit see also category germanium compounds elemental germanium starts to oxidize slowly in air at around 250 c forming geo 2 36 germanium is insoluble in dilute acids and alkalis but dissolves slowly in hot concentrated sulfuric and nitric acids and reacts violently with molten alkalis to produce germanates geo 3 2 germanium occurs mostly in the oxidation state 4 although many 2 compounds are known 37 other oxidation states are rare 3 is found in compounds such as ge 2 cl 6 and 3 and 1 are found on the surface of oxides 38 or negative oxidation states in germanides such as 4 in mg 2 ge germanium cluster anions zintl ions such as ge 4 2 ge 9 4 ge 9 2 ge 9 2 6 have been prepared by the extraction from alloys containing alkali metals and germanium in liquid ammonia in the presence of ethylenediamine or a cryptand 37 39 the oxidation states of the element in these ions are not integers similar to the ozonides o 3 two oxides of germanium are known germanium dioxide geo 2 germania and germanium monoxide geo 31 the dioxide geo 2 can be obtained by roasting germanium disulfide ges 2 and is a white powder that is only slightly soluble in water but reacts with alkalis to form germanates 31 the monoxide germanous oxide can be obtained by the high temperature reaction of geo 2 with ge metal 31 the dioxide and the related oxides and germanates exhibits the unusual property of having a high refractive index for visible light but transparency to infrared light 40 41 bismuth germanate bi 4 ge 3 o 12 bgo is used as a scintillator 42 binary compounds with other chalcogens are also known such as the di sulfide ges 2 di selenide gese 2 and the monosulfide ges selenide gese and telluride gete 37 ges 2 forms as a white precipitate when hydrogen sulfide is passed through strongly acid solutions containing ge iv 37 the disulfide is appreciably soluble in water and in solutions of caustic alkalis or alkaline sulfides nevertheless it is not soluble in acidic water which allowed winkler to discover the element 43 by heating the disulfide in a current of hydrogen the monosulfide ges is formed which sublimes in thin plates of a dark color and metallic luster and is soluble in solutions of the caustic alkalis 31 upon melting with alkaline carbonates and sulfur germanium compounds form salts known as thiogermanates 44 germane is similar to methane four tetra halides are known under normal conditions gei 4 is a solid gef 4 a gas and the others volatile liquids for example germanium tetrachloride gecl 4 is obtained as a colorless fuming liquid boiling at 83 1 c by heating the metal with chlorine 31 all the tetrahalides are readily hydrolyzed to hydrated germanium dioxide 31 gecl 4 is used in the production of organogermanium compounds 37 all four dihalides are known and in contrast to the tetrahalides are polymeric solids 37 additionally ge 2 cl 6 and some higher compounds of formula ge n cl 2 n 2 are known 31 the unusual compound ge 6 cl 16 has been prepared that contains the ge 5 cl 12 unit with a neopentane structure 45 germane geh 4 is a compound similar in structure to methane polygermanes compounds that are similar to alkanes with formula ge n h 2 n 2 containing up to five germanium atoms are known 37 the germanes are less volatile and less reactive than their corresponding silicon analogues 37 geh 4 reacts with alkali metals in liquid ammonia to form white crystalline mgeh 3 which contain the geh 3 anion 37 the germanium hydrohalides with one two and three halogen atoms are colorless reactive liquids 37 nucleophilic addition with an organogermanium compound the first organogermanium compound was synthesized by winkler in 1887 the reaction of germanium tetrachloride with diethylzinc yielded tetraethylgermane ge c 2 h 5 4 9 organogermanes of the type r 4 ge where r is an alkyl such as tetramethylgermane ge ch 3 4 and tetraethylgermane are accessed through the cheapest available germanium precursor germanium tetrachloride and alkyl nucleophiles organic germanium hydrides such as isobutylgermane ch 3 2 chch 2 geh 3 were found to be less hazardous and may be used as a liquid substitute for toxic germane gas in semiconductor applications many germanium reactive intermediates are known germyl free radicals germylenes similar to carbenes and germynes similar to carbynes 46 47 the organogermanium compound 2 carboxyethylgermasesquioxane was first reported in the 1970s and for a while was used as a dietary supplement and thought to possibly have anti tumor qualities 48 using a ligand called eind 1 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 co...