Germanium is a non-metal. Is germanium enough for your body: what is the use of a microelement, how to identify a shortage or excess
(Germanium; from lat. Germania - Germany), Ge - chemical. element of group IV of the periodic system of elements; at. n. 32, at. m. 72.59. Silvery-gray substance with a metallic sheen. In chem. compounds exhibits oxidation states + 2 and +4. Compounds with an oxidation state of +4 are more stable. Natural germanium consists of four stable isotopes with mass numbers 70 (20.55%), 72 (27.37%), 73(7.67%) and 74 (36.74%) and one radioactive isotope with mass number 76 ( 7.67%) and a half-life of 2,106 years. Artificially (with the help of various nuclear reactions) many radioactive isotopes have been obtained; the most important is the 71 Ge isotope with a half-life of 11.4 days.
The existence of holy germanium (under the name "ekasilitsiy") was predicted in 1871 by the Russian scientist D. I. Mendeleev. However, only in 1886 it. chemist K. Winkler discovered an unknown element in the mineral argyrodite, the properties of which coincided with the properties of "ecasilicon". Beginning of prom. the production of germanium dates back to the 40s. 20th century, when it was used as a semiconductor material. The content of germanium in the earth's crust (1-2) is 10~4%. Germanium is a trace element and is rarely found as its own minerals. Seven minerals are known, in which its concentration is more than 1%, among them: Cu2 (Cu, Ge, Ga, Fe, Zn) 2 (S, As) 4X X (6.2-10.2% Ge), rhenierite (Cu, Fe)2 (Cu, Fe, Ge, Ga, Zn)2 X X (S, As)4 (5.46-7.80% Ge) and argyrodite Ag8GeS6 (3/55-6.93% Ge) . G. also accumulates in caustobioliths (humic coals, oil shale, oil). The crystalline modification of diamond, stable under ordinary conditions, has a cubic structure like diamond, with a period a = 5.65753 A (Gel).
Germanium is
The density of germanium (t-ra 25 ° C) 5.3234 g / cm3, tmelt 937.2 ° C; tbp 2852°C; heat of fusion 104.7 cal/g, heat of sublimation 1251 cal/g, heat capacity (temperature 25°C) 0.077 cal/g deg; coefficient thermal conductivity, (t-ra 0 ° C) 0.145 cal / cm sec deg, temperature coefficient. linear expansion (t-ra 0-260 ° C), 5.8 x 10-6 deg-1. During melting, germanium decreases in volume (by about 5.6%), its density increases by 4% h. At high pressure, a diamond-like modification. Germanium undergoes polymorphic transformations, forming crystalline modifications: a tetragonal structure of the B-Sn type (GeII), a body-centered tetragonal structure with periods a = 5.93 A, c = 6.98 A (GeIII) and a body-centered cubic structure with a period a = 6, 92A(GeIV). These modifications are characterized by higher density and electrical conductivity compared to GeI.
Amorphous germanium can be obtained in the form of films (about 10-3 cm thick) by steam condensation. Its density is less than the density of crystalline G. The structure of energy zones in G. crystal determines its semiconductor properties. The width of the band gap G. is equal to 0.785 eV (t-ra 0 K), the electrical resistivity (t-ra 20 ° C) is 60 ohm cm, and with increasing temperature it decreases significantly according to an exponential law. Impurities give G. t. impurity conductivity of the electronic (impurities of arsenic, antimony, phosphorus) or hole (impurities of gallium, aluminum, indium) type. The mobility of charge carriers in G. (t-ra 25 ° C) for electrons is about 3600 cm2 / v sec, for holes - 1700 cm2 / v sec, the intrinsic concentration of charge carriers (t-ra 20 ° C) is 2.5. 10 13 cm-3. G. is diamagnetic. Upon melting, it transforms into a metallic state. Germanium is very brittle, its Mohs hardness is 6.0, microhardness is 385 kgf/mm2, compressive strength (temperature 20°C) is 690 kgf/cm2. With an increase in t-ry, hardness decreases, above t-ry 650 ° C, it becomes plastic, amenable to fur. processing. Germanium is practically inert to air, oxygen and to non-oxidizing electrolytes (if there is no dissolved oxygen) at temperatures up to 100 ° C. Resistant to the action of hydrochloric and dilute sulfuric acid; slowly dissolves in concentrated sulfuric and nitric acids when heated (the resulting film of dioxide slows down dissolution), dissolves well in aqua regia, in solutions of hypochlorites or alkali hydroxides (in the presence of hydrogen peroxide), in alkali melts, peroxides, nitrates and carbonates of alkali metals.
Above t-ry 600 ° C is oxidized in air and in a stream of oxygen, forming oxide GeO and dioxide (Ge02) with oxygen. Germanium oxide is a dark gray powder sublimating at t-re 710 ° C, slightly soluble in water with the formation of a weak germanite to-you (H2Ge02), a salt swarm (germanites) of low resistance. In to-takh GeO dissolves easily with the formation of salts of divalent H. Germanium dioxide is a white powder, exists in several polymorphic modifications that differ greatly in chemical. St. you: the hexagonal modification of dioxide is relatively well soluble in water (4.53 zU at t-re 25 ° C), alkali solutions and to-t, the tetragonal modification is practically insoluble in water and inert to acids. Dissolving in alkalis, the dioxide and its hydrate form salts of metagermanate (H2Ge03) and orthogermanate (H4Ge04) to-t - germanates. Alkali metal germanates dissolve in water, the remaining germanates are practically insoluble; freshly precipitated dissolve in mineral to-tah. G. easily combines with halogens, forming when heated (about t-ry 250 ° C) the corresponding tetrahalogenides - non-salt-like compounds that are easily hydrolyzed by water. G. are known - dark brown (GeS) and white (GeS2).
Germanium is characterized by compounds with nitrogen - brown nitride (Ge3N4) and black nitride (Ge3N2), characterized by a smaller chemical. tenacity. With phosphorus G. forms a low-resistant phosphide (GeP) of black color. It does not interact with carbon and does not alloy; it forms a continuous series of solid solutions with silicon. Germanium, as an analogue of carbon and silicon, is characterized by the ability to form germanohydrogens of the GenH2n + 2 type (germanes), as well as solid compounds of the GeH and GeH2 types (germenes). Germanium forms metal compounds () and with many others. metals. G.'s extraction from raw materials consists in receiving a rich germanium concentrate, and from it - high purity. In the prom. scale, germanium is obtained from tetrachloride, using its high volatility during purification (for isolation from concentrate), low in concentrated hydrochloric acid and high in organic solvents (for purification from impurities). Often for enrichment use high volatility of the lower sulfide and oxide G., to-rye are easily sublimated.
To obtain semiconductor germanium, directional crystallization and zone recrystallization are used. Monocrystalline germanium is obtained by drawing from the melt. In the process of growing G., special alloys are added. additives, adjusting certain properties of the monocrystal. G. is supplied in the form of ingots with a length of 380-660 mm and a cross section of up to 6.5 cm2. Germanium is used in radio electronics and electrical engineering as a semiconductor material for the manufacture of diodes and transistors. Lenses for infrared optics devices, nuclear radiation dosimeters, X-ray spectroscopy analyzers, sensors using the Hall effect, and converters of radioactive decay energy into electrical energy are made from it. Germanium is used in microwave attenuators, resistance thermometers, operated at a temperature of liquid helium. The G. film deposited on the reflector is distinguished by high reflectivity and good corrosion resistance. germanium with some metals, characterized by increased resistance to acidic aggressive environments, is used in instrument making, mechanical engineering and metallurgy. gemanium with gold form a low-melting eutectic and expand upon cooling. G.'s dioxide is used for the manufacture of special. glass, characterized by a high coefficient. refraction and transparency in the infrared part of the spectrum, glass electrodes and thermistors, as well as enamels and decorative glazes. Germanates are used as activators of phosphors and phosphors.
- a chemical element of the periodic system of chemical elements D.I. Mendeleev. And denoted by the symbol Ge, germanium is a simple substance that is gray-white in color and has solid characteristics like a metal.
The content in the earth's crust is 7.10-4% by weight. refers to trace elements, due to its reactivity to oxidation in the free state, it does not occur as a pure metal.
Finding germanium in nature
Germanium is one of the three chemical elements predicted by D.I. Mendeleev on the basis of their position in the periodic system (1871).
It belongs to rare trace elements.
At present, the main sources of industrial production of germanium are waste from zinc production, coal coking, ash from some certain types of coal, in silicate impurities, sedimentary iron rocks, nickel and tungsten ores, peat, oil, geothermal waters and some algae.
The main minerals containing germanium
Plumbohermatite (PbGeGa) 2 SO 4 (OH) 2 + H 2 O content up to 8.18%
yargyrodite AgGeS6 contains from 3.65 to 6.93% germany.
rhenierite Cu 3 (FeGeZn)(SAs) 4 contains from 5.5 to 7.8% germanium.
In some countries, obtaining germanium is a by-product of the processing of certain ores such as zinc-lead-copper. Germanium is also obtained in the production of coke, as well as in brown coal ash with a content of 0.0005 to 0.3% and in hard coal ash with a content of 0.001 to 1 -2%.
Germanium as a metal is very resistant to the action of atmospheric oxygen, oxygen, water, some acids, dilute sulfuric and hydrochloric acids. But concentrated sulfuric acid reacts very slowly.
Germanium reacts with nitric acid HNO 3 and aqua regia, slowly reacts with caustic alkalis to form a germanate salt, but with the addition of hydrogen peroxide H 2O2 the reaction is very fast.
When exposed to high temperatures above 700 °C, germanium is easily oxidized in air to form GeO 2 , readily reacts with halogens to form tetrahalides.
Does not react with hydrogen, silicon, nitrogen and carbon.
Volatile germanium compounds are known with the following characteristics:
Germany hexahydride-digermane, Ge 2 H 6 - combustible gas, decomposes during long-term storage in the light, turning yellow then brown turning into a dark brown solid, decomposed by water and alkalis.
Germany tetrahydride, monogermane - GeH 4 .
Application of germanium
Germanium, like some others, has the properties of so-called semiconductors. All according to their electrical conductivity are divided into three groups: conductors, semiconductors and insulators (dielectrics). The specific electrical conductivity of metals is in the range 10V4 - 10V6 Ohm.cmV-1, the division given is conditional. However, one can point out a fundamental difference in the electrophysical properties of conductors and semiconductors. For the former, the electrical conductivity decreases with increasing temperature, for semiconductors it increases. At temperatures close to absolute zero, semiconductors turn into insulators. As is known, metallic conductors exhibit the properties of superconductivity under such conditions.
Semiconductors can be various substances. These include: boron, (
Please note that germanium is taken by us in any quantity and form, incl. the form of scrap. You can sell germanium by calling the telephone number in Moscow indicated above.
Germanium is a brittle, silvery-white semimetal discovered in 1886. This mineral is not found in its pure form. It is found in silicates, iron and sulfide ores. Some of its compounds are toxic. Germanium was widely used in the electrical industry, where its semiconductor properties came in handy. It is indispensable in the production of infrared and fiber optics.
What are the properties of germanium
This mineral has a melting point of 938.25 degrees Celsius. The indicators of its heat capacity still cannot be explained by scientists, which makes it indispensable in many areas. Germanium has the ability to increase its density when melted. It has excellent electrical properties, which makes it an excellent indirect-gap semiconductor.
If we talk about the chemical properties of this semimetal, it should be noted that it is resistant to acids and alkalis, water and air. Germanium dissolves in a solution of hydrogen peroxide and aqua regia.
mining germanium
Now a limited amount of this semi-metal is mined. Its deposits are much smaller compared to those of bismuth, antimony, and silver.
Due to the fact that the proportion of the content of this mineral in the earth's crust is quite small, it forms its own minerals due to the introduction of other metals into the crystal lattices. The highest content of germanium is observed in sphalerite, pyrargyrite, sulfanite, in non-ferrous and iron ores. It occurs, but much less frequently, in oil and coal deposits.
Use of germanium
Despite the fact that germanium was discovered quite a long time ago, it began to be used in industry about 80 years ago. Semi-metal was first used in military production for the manufacture of some electronic devices. In this case, it found use as diodes. Now the situation has changed somewhat.
The most popular areas of application of germanium include:
- optics production. Semimetal has become indispensable in the manufacture of optical elements, which include optical windows of sensors, prisms, and lenses. Here, the transparency properties of germanium in the infrared region came in handy. Semimetal is used in the production of optics for thermal imaging cameras, fire systems, night vision devices;
- production of radio electronics. In this area, semi-metal was used in the manufacture of diodes and transistors. However, in the 1970s, germanium devices were replaced by silicon ones, since silicon made it possible to significantly improve the technical and operational characteristics of manufactured products. Increased resistance to temperature effects. In addition, germanium devices emitted a lot of noise during operation.
The current situation with Germany
Currently, semimetal is used in the production of microwave devices. Telleride germanium has proven itself as a thermoelectric material. Germanium prices are now quite high. One kilogram of metallic germanium costs $1,200.
Buying Germany
Silver gray germanium is rare. The brittle semimetal is distinguished by its semiconductor properties and is widely used to create modern electrical appliances. It is also used to create high-precision optical instruments and radio equipment. Germanium is of great value both in the form of a pure metal and in the form of dioxide.
The Goldform company specializes in the purchase of germanium, various scrap metal, and radio components. We offer assistance with the assessment of the material, with transportation. You can mail germanium and get your money back in full.
Germanium is a chemical element with atomic number 32 in the periodic system, denoted by the symbol Ge (Ger. Germanium).
The history of the discovery of germanium
The existence of the element ekasilicium, an analogue of silicon, was predicted by D.I. Mendeleev back in 1871. And in 1886, one of the professors of the Freiberg Mining Academy discovered a new silver mineral - argyrodite. This mineral was then given to the professor of technical chemistry Clemens Winkler for a complete analysis.
This was not done by chance: 48-year-old Winkler was considered the best analyst of the academy.
Quite quickly, he found out that silver in the mineral is 74.72%, sulfur - 17.13, mercury - 0.31, ferrous oxide - 0.66, zinc oxide - 0.22%. And almost 7% of the weight of the new mineral was accounted for by some incomprehensible element, most likely still unknown. Winkler singled out the unidentified component of the argyrodite, studied its properties and realized that he had indeed found a new element - the explication predicted by Mendeleev. This is a brief history of the element with atomic number 32.
However, it would be wrong to think that Winkler's work went smoothly, without a hitch, without a hitch. Here is what Mendeleev writes about this in the supplements to the eighth chapter of Fundamentals of Chemistry: “At first (February 1886), the lack of material, the absence of a spectrum in the burner flame, and the solubility of many germanium compounds hindered Winkler’s research ...” Pay attention to the “lack of spectrum in the flame. How so? Indeed, in 1886 the method of spectral analysis already existed; Rubidium, cesium, thallium, indium have already been discovered on Earth by this method, and helium on the Sun. Scientists knew for sure that each chemical element has a completely individual spectrum, and suddenly there is no spectrum!
The explanation came later. Germanium has characteristic spectral lines - with a wavelength of 2651.18, 3039.06 Ǻ and a few more. But they all lie in the invisible ultraviolet part of the spectrum, and it can be considered fortunate that Winkler's adherence to traditional methods of analysis - they led to success.
Winkler's method for isolating germanium is similar to one of the current industrial methods for obtaining element No. 32. First, the germanium contained in the argarite was converted into dioxide, and then this white powder was heated to 600...700°C in a hydrogen atmosphere. The reaction is obvious: GeO 2 + 2H 2 → Ge + 2H 2 O.
Thus, relatively pure germanium was obtained for the first time. Winkler initially intended to name the new element neptunium, after the planet Neptune. (Like element #32, this planet was predicted before it was discovered.) But then it turned out that such a name had previously been assigned to one falsely discovered element, and, not wanting to compromise his discovery, Winkler abandoned his first intention. He did not accept the proposal to call the new element angular, i.e. “angular, controversial” (and this discovery really caused a lot of controversy). True, the French chemist Rayon, who put forward such an idea, later said that his proposal was nothing more than a joke. Winkler named the new element germanium after his country, and the name stuck.
Finding germanium in natureIt should be noted that in the course of the geochemical evolution of the earth's crust, a significant amount of germanium was washed out from most of the land surface into the oceans, therefore, at present, the amount of this trace element contained in the soil is extremely insignificant.
The total content of germanium in the earth's crust is 7 × 10 −4% by mass, that is, more than, for example, antimony, silver, bismuth. Germanium, due to its insignificant content in the earth's crust and geochemical affinity with some widespread elements, exhibits a limited ability to form its own minerals, dispersing in the lattices of other minerals. Therefore, germanium's own minerals are extremely rare. Almost all of them are sulfosalts: germanite Cu 2 (Cu, Fe, Ge, Zn) 2 (S, As) 4 (6 - 10% Ge), argyrodite Ag 8 GeS 6 (3.6 - 7% Ge), confildite Ag 8 (Sn, Ge) S 6 (up to 2% Ge), etc. The bulk of germanium is dispersed in the earth's crust in a large number of rocks and minerals. So, for example, in some sphalerites, the content of germanium reaches kilograms per ton, in enargites up to 5 kg/t, in pyrargyrite up to 10 kg/t, in sulvanite and frankeite 1 kg/t, in other sulfides and silicates - hundreds and tens of g/t. t. Germanium is concentrated in deposits of many metals - in sulfide ores of non-ferrous metals, in iron ores, in some oxide minerals (chromite, magnetite, rutile, etc.), in granites, diabases and basalts. In addition, germanium is present in almost all silicates, in some deposits of coal and oil.
Receipt GermanyGermanium is obtained mainly from by-products of processing non-ferrous metal ores (zinc blende, zinc-copper-lead polymetallic concentrates) containing 0.001-0.1% Germany. Ash from coal combustion, dust from gas generators and waste from coke plants are also used as raw materials. Initially, germanium concentrate (2-10% Germany) is obtained from the listed sources in various ways, depending on the composition of the raw material. The extraction of germanium from concentrate usually involves the following steps:
1) chlorination of the concentrate with hydrochloric acid, its mixture with chlorine in an aqueous medium or other chlorinating agents to obtain technical GeCl 4 . To purify GeCl 4, rectification and extraction of impurities with concentrated HCl are used.
2) Hydrolysis of GeCl 4 and calcination of hydrolysis products to obtain GeO 2 .
3) Reduction of GeO 2 with hydrogen or ammonia to metal. To isolate very pure germanium, which is used in semiconductor devices, metal is melted by zone. Single-crystal germanium, necessary for the semiconductor industry, is usually obtained by zone melting or by the Czochralski method.
GeO 2 + 4H 2 \u003d Ge + 2H 2 O
Semiconductor purity germanium with an impurity content of 10 -3 -10 -4% is obtained by zone melting, crystallization or thermolysis of the volatile GeH 4 monogermane:
GeH 4 \u003d Ge + 2H 2,
which is formed during the decomposition of compounds of active metals with Ge - germanides by acids:
Mg 2 Ge + 4HCl \u003d GeH 4 - + 2MgCl 2
Germanium occurs as an admixture in polymetallic, nickel, and tungsten ores, as well as in silicates. As a result of complex and time-consuming operations for the enrichment of ore and its concentration, germanium is isolated in the form of GeO 2 oxide, which is reduced with hydrogen at 600 ° C to a simple substance:
GeO 2 + 2H 2 \u003d Ge + 2H 2 O.
Purification and growth of germanium single crystals is carried out by zone melting.
Pure germanium dioxide was obtained for the first time in the USSR in early 1941. It was used to make germanium glass with a very high refractive index. Research on element No. 32 and methods for its possible production resumed after the war, in 1947. Now germanium was then of interest to Soviet scientists precisely as a semiconductor.
Physical properties GermanyIn appearance, germanium is easily confused with silicon.
Germanium crystallizes in a diamond-type cubic structure, unit cell parameter a = 5.6575Å.
This element is not as strong as titanium or tungsten. The density of solid Germanium is 5.327 g/cm 3 (25°C); liquid 5.557 (1000°C); t pl 937.5°C; bp about 2700°C; thermal conductivity coefficient ~60 W/(m K), or 0.14 cal/(cm sec deg) at 25°C.
Germanium is almost as brittle as glass and can behave accordingly. Even at ordinary temperature, but above 550 ° C, it is amenable to plastic deformation. Hardness Germany on a mineralogical scale 6-6,5; compressibility coefficient (in the pressure range 0-120 Gn/m 2 , or 0-12000 kgf/mm 2) 1.4 10 -7 m 2 /mn (1.4 10 -6 cm 2 /kgf); surface tension 0.6 N/m (600 dynes/cm). Germanium is a typical semiconductor with a band gap of 1.104 10 -19 J or 0.69 eV (25°C); electrical resistivity high purity Germany 0.60 ohm-m (60 ohm-cm) at 25°C; the mobility of electrons is 3900 and the mobility of holes is 1900 cm 2 /v sec (25 ° C) (with an impurity content of less than 10 -8%).
All "unusual" modifications of crystalline germanium are superior to Ge-I and electrical conductivity. The mention of this particular property is not accidental: the value of electrical conductivity (or reciprocal value - resistivity) is especially important for a semiconductor element.
Chemical properties GermanyIn chemical compounds, germanium usually exhibits valences of 4 or 2. Compounds with a valence of 4 are more stable. Under normal conditions, it is resistant to air and water, alkalis and acids, soluble in aqua regia and in an alkaline solution of hydrogen peroxide. Germanium alloys and glasses based on germanium dioxide are used.
In chemical compounds, germanium usually exhibits valences of 2 and 4, with compounds of 4-valent germanium being more stable. At room temperature, germanium is resistant to air, water, alkali solutions, and dilute hydrochloric and sulfuric acids, but readily dissolves in aqua regia and in an alkaline solution of hydrogen peroxide. Nitric acid slowly oxidizes. When heated in air to 500-700°C, germanium is oxidized to GeO and GeO 2 oxides. Germany oxide (IV) - white powder with t pl 1116°C; solubility in water 4.3 g/l (20°C). According to its chemical properties, it is amphoteric, soluble in alkalis and with difficulty in mineral acids. It is obtained by calcining the hydrated precipitate (GeO 3 nH 2 O) released during the hydrolysis of GeCl 4 tetrachloride. Fusion of GeO 2 with other oxides can be obtained derivatives of germanic acid - metal germanates (Li 2 GeO 3 , Na 2 GeO 3 and others) - solids with high melting points.
When germanium reacts with halogens, the corresponding tetrahalides are formed. The reaction proceeds most easily with fluorine and chlorine (already at room temperature), then with bromine (weak heating) and iodine (at 700-800°C in the presence of CO). One of the most important compounds Germany GeCl 4 tetrachloride is a colorless liquid; t pl -49.5°C; bp 83.1°C; density 1.84 g/cm 3 (20°C). Water strongly hydrolyzes with the release of a precipitate of hydrated oxide (IV). It is obtained by chlorination of metallic Germany or by the interaction of GeO 2 with concentrated HCl. Also known are Germany dihalides of the general formula GeX 2 , GeCl monochloride, Ge 2 Cl 6 hexachlorodigermane, and Germany oxychlorides (for example, CeOCl 2).
Sulfur reacts vigorously with Germany at 900-1000°C to form GeS 2 disulfide, a white solid, mp 825°C. GeS monosulfide and similar compounds of Germany with selenium and tellurium, which are semiconductors, are also described. Hydrogen slightly reacts with germanium at 1000-1100°C to form germine (GeH) X, an unstable and easily volatile compound. By reacting germanides with dilute hydrochloric acid, germanohydrogens of the series Ge n H 2n+2 up to Ge 9 H 20 can be obtained. Germylene composition GeH 2 is also known. Germanium does not directly react with nitrogen, however, there is Ge 3 N 4 nitride, which is obtained by the action of ammonia on Germanium at 700-800°C. Germanium does not interact with carbon. Germanium forms compounds with many metals - germanides.
Numerous complex compounds of germany are known, which are becoming increasingly important both in the analytical chemistry of germanium and in the processes of its preparation. Germanium forms complex compounds with organic hydroxyl-containing molecules (polyhydric alcohols, polybasic acids, and others). Heteropolyacids Germany were obtained. As well as for other elements of group IV, Germany is characterized by the formation of organometallic compounds, an example of which is tetraethylgermane (C 2 H 5) 4 Ge 3.
Compounds of divalent germanium.Germanium(II) hydride GeH 2 . White unstable powder (in air or in oxygen it decomposes with an explosion). Reacts with alkalis and bromine.
Germanium (II) monohydride polymer (polygermine) (GeH 2) n . Brownish black powder. Poorly soluble in water, instantly decomposes in air and explodes when heated to 160 ° C in a vacuum or in an inert gas atmosphere. Formed during the electrolysis of sodium germanide NaGe.
Germanium(II) oxide GeO. Black crystals with basic properties. Decomposes at 500°C into GeO 2 and Ge. Slowly oxidizes in water. Slightly soluble in hydrochloric acid. Shows restorative properties. Obtained by the action of CO 2 on metallic germanium, heated to 700-900 ° C, alkalis - on germanium (II) chloride, by calcining Ge (OH) 2 or by reducing GeO 2.
Germanium hydroxide (II) Ge (OH) 2. Red-orange crystals. When heated, it turns into GeO. Shows amphoteric character. Obtained by treatment of germanium (II) salts with alkalis and hydrolysis of germanium (II) salts.
Germanium(II) fluoride GeF 2 . Colorless hygroscopic crystals, t pl =111°C. Obtained by the action of GeF 4 vapors on germanium metal when heated.
Germanium (II) chloride GeCl 2 . Colorless crystals. t pl \u003d 76.4 ° C, t bp \u003d 450 ° C. At 460°С, it decomposes into GeCl 4 and metallic germanium. Hydrolyzed by water, slightly soluble in alcohol. Obtained by the action of GeCl 4 vapors on germanium metal when heated.
Germanium (II) bromide GeBr 2. Transparent needle crystals. t pl \u003d 122 ° C. Hydrolyzes with water. Slightly soluble in benzene. Soluble in alcohol, acetone. Obtained by the interaction of germanium (II) hydroxide with hydrobromic acid. When heated, it disproportionates into metallic germanium and germanium (IV) bromide.
Germanium (II) iodide GeI 2 . Yellow hexagonal plates, diamagnetic. t pl =460 about C. Slightly soluble in chloroform and carbon tetrachloride. When heated above 210°C, it decomposes into metallic germanium and germanium tetraiodide. Obtained by the reduction of germanium (II) iodide with hypophosphoric acid or by thermal decomposition of germanium tetraiodide.
Germanium(II) sulfide GeS. Received by dry way - greyish-black brilliant rhombic opaque crystals. t pl \u003d 615 ° C, density is 4.01 g / cm 3. Slightly soluble in water and ammonia. Soluble in potassium hydroxide. Received wet - red-brown amorphous precipitate, the density is 3.31 g/cm 3 . Soluble in mineral acids and ammonium polysulfide. Obtained by heating germanium with sulfur or passing hydrogen sulfide through a germanium (II) salt solution.
Compounds of tetravalent germanium.Germanium(IV) hydride GeH 4 . Colorless gas (density is 3.43 g/cm 3 ). It is poisonous, smells very unpleasant, boils at -88 o C, melts at about -166 o C, thermally dissociates above 280 o C. Passing GeH 4 through a heated tube, a shiny mirror of metallic germanium is obtained on its walls. Obtained by the action of LiAlH 4 on germanium (IV) chloride in ether or by treating a solution of germanium (IV) chloride with zinc and sulfuric acid.
Germanium oxide (IV) GeO 2. It exists in the form of two crystalline modifications (hexagonal with a density of 4.703 g / cm 3 and tetrahedral with a density of 6.24 g / cm 3). Both are air resistant. Slightly soluble in water. t pl \u003d 1116 ° C, t kip \u003d 1200 ° C. Shows amphoteric character. It is reduced by aluminum, magnesium, carbon to metallic germanium when heated. Obtained by synthesis from elements, calcination of germanium salts with volatile acids, oxidation of sulfides, hydrolysis of germanium tetrahalides, treatment of alkali metal germanites with acids, metallic germanium with concentrated sulfuric or nitric acids.
Germanium (IV) fluoride GeF 4 . A colorless gas that smokes in air. t pl \u003d -15 about C, t kip \u003d -37 ° C. Hydrolyzes with water. Obtained by decomposition of barium tetrafluorogermanate.
Germanium (IV) chloride GeCl 4 . Colorless liquid. t pl \u003d -50 o C, t kip \u003d 86 o C, density is 1.874 g / cm 3. Hydrolyzed by water, soluble in alcohol, ether, carbon disulfide, carbon tetrachloride. Obtained by heating germanium with chlorine and passing hydrogen chloride through a suspension of germanium oxide (IV).
Germanium (IV) bromide GeBr 4 . Octahedral colorless crystals. t pl \u003d 26 o C, t kip \u003d 187 o C, density is 3.13 g / cm 3. Hydrolyzes with water. Soluble in benzene, carbon disulfide. Obtained by passing bromine vapor over heated metallic germanium or by the action of hydrobromic acid on germanium (IV) oxide.
Germanium (IV) iodide GeI 4 . Yellow-orange octahedral crystals, t pl \u003d 146 ° C, t kip \u003d 377 ° C, density is 4.32 g / cm 3. At 445 ° C, it decomposes. Soluble in benzene, carbon disulfide, and hydrolyzed by water. In air, it gradually decomposes into germanium (II) iodide and iodine. Attaches ammonia. Obtained by passing iodine vapor over heated germanium or by the action of hydroiodic acid on germanium (IV) oxide.
Germanium (IV) sulfide GeS 2. White crystalline powder, t pl \u003d 800 ° C, density is 3.03 g / cm 3. Slightly soluble in water and slowly hydrolyzes in it. Soluble in ammonia, ammonium sulfide and alkali metal sulfides. It is obtained by heating germanium (IV) oxide in a stream of sulfur dioxide with sulfur or by passing hydrogen sulfide through a solution of germanium (IV) salt.
Germanium sulfate (IV) Ge (SO 4) 2. Colorless crystals, density is 3.92 g/cm 3 . It decomposes at 200 o C. It is reduced by coal or sulfur to sulfide. Reacts with water and alkali solutions. Obtained by heating germanium (IV) chloride with sulfur oxide (VI).
Isotopes of germaniumThere are five isotopes found in nature: 70 Ge (20.55% wt.), 72 Ge (27.37%), 73 Ge (7.67), 74 Ge (36.74%), 76 Ge (7.67% ). The first four are stable, the fifth (76 Ge) undergoes double beta decay with a half-life of 1.58×10 21 years. In addition, there are two "long-lived" artificial ones: 68 Ge (half-life 270.8 days) and 71 Ge (half-life 11.26 days).
Application of germanium
Germanium is used in the manufacture of optics. Due to its transparency in the infrared region of the spectrum, ultra-high purity metallic germanium is of strategic importance in the production of optical elements for infrared optics. In radio engineering, germanium transistors and detector diodes have characteristics different from silicon ones, due to the lower pn-junction trigger voltage in germanium - 0.4V versus 0.6V for silicon devices.
For more details, see the article application of germanium.
The biological role of germaniumGermanium is found in animals and plants. Small amounts of germanium have no physiological effect on plants, but are toxic in large amounts. Germanium is non-toxic to molds.
For animals, germanium has low toxicity. Germanium compounds have not been found to have a pharmacological effect. The permissible concentration of germanium and its oxide in the air is 2 mg / m³, that is, the same as for asbestos dust.
Divalent germanium compounds are much more toxic.
In experiments determining the distribution of organic germanium in the body 1.5 hours after its oral administration, the following results were obtained: a large amount of organic germanium is found in the stomach, small intestine, bone marrow, spleen, and blood. Moreover, its high content in the stomach and intestines shows that the process of its absorption into the blood has a prolonged effect.
The high content of organic germanium in the blood allowed Dr. Asai to put forward the following theory of the mechanism of its action in the human body. It is assumed that organic germanium in the blood behaves similarly to hemoglobin, which also carries a negative charge and, like hemoglobin, participates in the process of oxygen transfer in body tissues. This prevents the development of oxygen deficiency (hypoxia) at the tissue level. Organic germanium prevents the development of the so-called blood hypoxia, which occurs when the amount of hemoglobin capable of attaching oxygen decreases (a decrease in the oxygen capacity of the blood), and develops with blood loss, carbon monoxide poisoning, and radiation exposure. The most sensitive to oxygen deficiency are the central nervous system, the heart muscle, the tissues of the kidneys, and the liver.
As a result of the experiments, it was also found that organic germanium promotes the induction of gamma interferons, which suppress the reproduction of rapidly dividing cells and activate specific cells (T-killers). The main areas of action of interferons at the body level are antiviral and antitumor protection, immunomodulatory and radioprotective functions of the lymphatic system.
In the process of studying pathological tissues and tissues with primary signs of disease, it was found that they are always characterized by a lack of oxygen and the presence of positively charged hydrogen radicals H + . H + ions have an extremely negative effect on the cells of the human body, up to their death. Oxygen ions, having the ability to combine with hydrogen ions, make it possible to selectively and locally compensate for damage to cells and tissues caused by hydrogen ions. The action of germanium on hydrogen ions is due to its organic form - the form of sesquioxide. In preparing the article, materials of Suponenko A.N. were used.
DEFINITION
Germanium is the thirty-second element of the Periodic Table. Designation - Ge from the Latin "germanium". Located in the fourth period, IVA group. Refers to semimetals. The nuclear charge is 32.
In the compact state, germanium has a silvery color (Fig. 1) and looks like a metal in appearance. At room temperature, it is resistant to air, oxygen, water, hydrochloric and dilute sulfuric acids.
Rice. 1. Germanium. Appearance.
Atomic and molecular weight of germanium
DEFINITION
Relative molecular weight of a substance (M r) is a number showing how many times the mass of a given molecule is greater than 1/12 of the mass of a carbon atom, and relative atomic mass of an element (A r)- how many times the average mass of atoms of a chemical element is greater than 1/12 of the mass of a carbon atom.
Since germanium exists in the free state in the form of monatomic Ge molecules, the values of its atomic and molecular masses coincide. They are equal to 72.630.
Isotopes of germanium
It is known that germanium can occur in nature in the form of five stable isotopes 70 Ge (20.55%), 72 Ge (20.55%), 73 Ge (7.67%), 74 Ge (36.74%) and 76 Ge (7.67%). Their mass numbers are 70, 72, 73, 74 and 76, respectively. The nucleus of the germanium isotope 70 Ge contains thirty-two protons and thirty-eight neutrons, the remaining isotopes differ from it only in the number of neutrons.
There are artificial unstable radioactive isotopes of germanium with mass numbers from 58 to 86, among which the 68 Ge isotope with a half-life of 270.95 days is the longest-lived.
germanium ions
On the outer energy level of the germanium atom, there are four electrons that are valence:
1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 2 .
As a result of chemical interaction, germanium gives up its valence electrons, i.e. is their donor, and turns into a positively charged ion:
Ge 0 -2e → Ge 2+;
Ge 0 -4e → Ge 4+ .
Molecule and atom of germanium
In the free state, germanium exists in the form of monatomic Ge molecules. Here are some properties that characterize the germanium atom and molecule:
Examples of problem solving
EXAMPLE 1
EXAMPLE 2
| Exercise | Calculate the mass fractions of the elements that make up germanium (IV) oxide if its molecular formula is GeO 2 . |
| Solution | The mass fraction of an element in the composition of any molecule is determined by the formula: ω (X) = n × Ar (X) / Mr (HX) × 100%. |
In 1870 D.I. Mendeleev, on the basis of the periodic law, predicted an as yet undiscovered element of group IV, calling it ekasilicium, and described its main properties. In 1886, the German chemist Clemens Winkler, during a chemical analysis of the mineral argyrodite, discovered this chemical element. Initially, Winkler wanted to name the new element "neptunium", but this name had already been given to one of the proposed elements, so the element was named after the scientist's homeland - Germany.
Being in nature, getting:
Germanium is found in sulfide ores, iron ore, and is found in almost all silicates. The main minerals containing germanium: argyrodite Ag 8 GeS 6, confieldite Ag 8 (Sn,Ce)S 6, stottite FeGe(OH) 6, germanite Cu 3 (Ge,Fe,Ga)(S,As) 4, rhenierite Cu 3 ( Fe,Ge,Zn)(S,As) 4 .
As a result of complex and time-consuming operations for enrichment of ore and its concentration, germanium is isolated in the form of GeO 2 oxide, which is reduced with hydrogen at 600°C to a simple substance.
GeO 2 + 2H 2 \u003d Ge + 2H 2 O
Germanium is purified by zone melting, which makes it one of the most chemically pure materials.
Physical properties:
Gray-white solid with a metallic luster (mp 938°C, bp 2830°C)
Chemical properties:
Under normal conditions, germanium is resistant to air and water, alkalis and acids, it dissolves in aqua regia and in an alkaline solution of hydrogen peroxide. The oxidation states of germanium in its compounds: 2, 4.
The most important connections:
Germanium(II) oxide, GeO, grey-black, slightly sol. in-in, when heated, it disproportionates: 2GeO \u003d Ge + GeO 2
Germanium(II) hydroxide Ge(OH) 2 , red-orange. crystal,
germanium(II) iodide, GeI 2 , yellow cr., sol. in water, hydrol. bye.
Germanium(II) hydride, GeH 2 , tv. white por., easily oxidized. and decay.
Germanium(IV) oxide, GeO 2 , white crystals, amphoteric, obtained by hydrolysis of chloride, sulfide, germanium hydride, or by the reaction of germanium with nitric acid.
Germanium(IV) hydroxide, (germanic acid), H 2 GeO 3 , weak. unst. biaxial to-ta, germanate salts, for example. sodium germanate, Na 2 GeO 3 , white crystal, sol. in water; hygroscopic. There are also Na 2 hexahydroxogermanates (ortho-germanates), and polygermanates
Germanium(IV) sulfate, Ge(SO 4) 2 , colorless. cr., hydrolyzed by water to GeO 2, obtained by heating germanium (IV) chloride with sulfuric anhydride at 160 ° C: GeCl 4 + 4SO 3 \u003d Ge (SO 4) 2 + 2SO 2 + 2Cl 2
Germanium(IV) halides, fluoride GeF 4 - bests. gas, raw hydrol., reacts with HF, forming H 2 - germanofluoric acid: GeF 4 + 2HF \u003d H 2,
chloride GeCl 4 , colorless. liquid, hydr., bromide GeBr 4 , ser. cr. or colorless. liquid, sol. in org. conn.,
iodide GeI 4, yellow-orange. cr., slow. hydr., sol. in org. conn.
Germanium(IV) sulfide, GeS 2 , white kr., poorly sol. in water, hydrol., reacts with alkalis:
3GeS 2 + 6NaOH = Na 2 GeO 3 + 2Na 2 GeS 3 + 3H 2 O, forming germanates and thiogermanates.
Germanium(IV) hydride, "german", GeH 4 , colorless gas, organic derivatives of tetramethylgermane Ge(CH 3) 4 , tetraethylgermane Ge(C 2 H 5) 4 - colorless. liquids.
Application:
The most important semiconductor material, the main areas of application: optics, radio electronics, nuclear physics.
Germanium compounds are slightly toxic. Germanium is a microelement that in the human body increases the efficiency of the body's immune system, fights cancer, and reduces pain. It is also noted that germanium promotes the transfer of oxygen to the tissues of the body and is a powerful antioxidant - a blocker of free radicals in the body.
The daily requirement of the human body is 0.4–1.5 mg.
Garlic is the champion in germanium content among food products (750 micrograms of germanium per 1 g of dry mass of garlic cloves).
The material was prepared by students of the Institute of Physics and Chemistry of Tyumen State University
Demchenko Yu.V., Bornovolokova A.A.
Sources:
Germanium//Wikipedia./ URL: http://ru.wikipedia.org/?oldid=63504262 (date of access: 06/13/2014).
Germanium//Allmetals.ru/URL: http://www.allmetals.ru/metals/germanium/ (date of access: 06/13/2014).
