Bài giảng Hóa học - Chương 4: Oxygen Family - Calcogens (2)

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GROUP VIA Oxygen O Oxygen Family - Calcogens 1. Đặc điểm chung Sulfur S 2. Oxygen Selenium Se  Tính chất lý học  Tính chất hóa học Tellurium Te  Vai trò sinh học Polonium Po  Trạng thái tự nhiên, điều chế và ứng dụng  Ozon  Oxide  Hydroxide  Hydro peoxide 1. Lưu huỳnh  Đơn chất  Hợp chất S(-II)  Hợp chất S(IV)  Hợp chất S(VI) 1  Một số hợp chất khác của lưu huỳnh Department of Inorganic Chemistry - HUT
2 Department of Inorganic Chemistry - HUT
Sulfur – S [Ne]3s 3p 2 4 Sulfur is a nonmetallic solid. Occurs free in nature as S8. S used in sulfuric acid, H2SO4 and in making tires. Sulfur compounds are used in bleaching fruit and 3 grain. Department of Inorganic Chemistry - HUT
95.30 C 1190 C 2000 C 444.70 C Sα ﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈ S β ﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈ Sλ ﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈ S µ ﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈ S1(2gas ) 1 4 4 2 4 43 1 4 4 2 4 43 3 Solid Liquid S8 , S 2 , S rhombic monoclinic monoclinic hệ trực thoi hệ một nghiêng hệ một nghiêng 1 4 4 4 4 44 2 4 4 4 4 4 43 14 2 43 S8 Sn 200 oC, đặc quánh 440 oC, linh động 160 oC, nhớt Hơi R R 4
Màu vàng Vàng nhạt d=2.06 g/cm3 d=1.96 g/cm3 Mp=112.8 oC Mp=119.2 oC 95.30 C Sα ﾈﾈﾈﾈ∆Hﾈﾈ0 =ﾈﾈ0.401 ﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈ S β kJ / mol 5 Department of Inorganic Chemistry - HUT
Sα Sβ Sα Sβ 6 Department of Inorganic Chemistry - HUT
Tính chất hóa học: -Là nguyên tố tương đối hoạt động: ở nhiệt độ thường hơi kém hoạt động, khi đun nóng có phản ứng với hầu hết nguyên tố trừ khí trơ, N, I, Au, Pt. -Tính oxi hóa: tác dụng với hydro; kim loại kiềm, kiềm thổ, Ag, Hg ở nhiệt độ thấp; Ni, Co, Cr ở nhiệt độ cao. o o 300 C , ∆H =−20.08 kJ Sα + H 2 ﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈﾈ H 2 S 7 Department of Inorganic Chemistry - HUT
Tính chất hóa học: -Tính khử: cháy trong oxy; tác dụng F ở nhiệt độ thường; Cl, Br khi đun nóng; P ở 100 oC; KNO3, KClO3, K2Cr2O7, HNO3, H2SO4 đặc. o burn , ∆H =−297 kJ S + O2 SO2 3S + 2 KClO3 = 2 KCl + 3SO2 S + 2 H 2 SO4 = 2 H 2O + 3SO2 8 Department of Inorganic Chemistry - HUT
Tính chất hóa học: -Tính vừa oxi hóa vừa khử: tan trong kiềm đặc, kiềm nóng chảy, sunfua, sunfit. 3S + 6 NaOH = 2 Na2 S + Na2 SO3 + 3H 2O 2− 2− S + nS = S n +1 2− 2− SO + S = S 2 O 3 3 9 Department of Inorganic Chemistry - HUT
APPLICATIONS Sulfur has many industrial uses. Through its major derivative, sulfuric acid , sulfur ranks as one of the more important elements used as an industrial raw material. It is of prime importance to every sector of the world's economies. Sulfuric acid production is the major end use for sulfur, and consumption of sulfuric acid has been regarded as one of the best indices of a nation's industrial development. More sulfuric acid is produced in the US every year than any other industrial chemical. Sulfur is also used in batteries, detergents, the vulcanization of rubber, fungicides, and in the manufacture of phosphate fertilizers. Sulfites are used to bleach paper and as a preservative in wine and dried fruit. Because of its flammable nature, sulfur also finds use in matches, gunpowder, and fireworks. Sodium or ammonium thiosulfate is used as photographic fixing agents. Magnesium sulfate, better known as Epsom salts, can be used as a laxative, a bath additive, an exfoliant, or a magnesium supplement for plants. Sulfur is used as the lightgenerating medium in the rare lighting fixtures known as sulfur lamps. In the late 1700s, furniture makers used molten sulfur to produce decorative inlays in their craft. Because of the sulfur dioxide produced during the process of melting sulfur, 10 the craft of sulfur inlays was soon abandoned. Department of Inorganic Chemistry - HUT
HISTORY Sulfur (Sanskrit, sulvere; Latin sulpur) was known in ancient times, and is referred to in the Biblical Pentateuch (Genesis). The word itself is almost certainly from the Arabic sufra meaning yellow, from the bright color of the naturally occurring form. English translations of the Bible commonly refer to sulfur as "brimstone", giving rise to the name of 'Fire and brimstone' sermons, in which listeners are reminded of the fate of eternal damnation that awaits the nonbelieving and unrepented. It is from this part of the Bible that Hell is implied to "smell of sulfur", although as mentioned above sulfur is in fact odorless. The "smell of sulfur" usually refers to the odor of hydrogen sulfide, e.g. from rotten eggs. Burning sulfur produces sulfur dioxide, the smell associated with burnt matches. Homer mentioned "pestaverting sulfur" in the 8th century BC and in 424 BC, the tribe of Boeotia destroyed the walls of a city by burning a mixture of coal, sulfur, and tar under them. Sometime in the 12th century, the Chinese invented gun powder which is a mixture of potassium nitrate (KNO3), carbon, and sulfur. Early alchemists gave sulfur its own alchemical symbol which was a triangle at the top of a cross. In the late 1770s, Antoine Lavoisier helped convince the scientific community that sulfur was an element and not a compound. In 1867, sulfur was discovered in underground deposits in Louisiana and Texas. The overlying layer of earth was quicksand, prohibiting ordinary 11 mining operations. Therefore the Frasch process was utilized
OCCURRENCE Sulfur Sulfur crystalites at Waiotapu hot springs, New Zealand Elemental sulfur can be found near hot springs and volcanic regions in many parts of the world, especially along the Pacific Ring of Fire. Such volcanic deposits are currently exploited in Indonesia, Chile, and Japan. Significant desposits of elemental sulfur also exist in salt domes along the coast of the Gulf of Mexico, and in evaporites in eastern Europe and western Asia. The sulfur in these deposits is believed to come from the action of anaerobic bacteria on sulfate minerals, especially gypsum. Such deposits are the basis for commercial production in the United States, Poland, Russia, Turkmenistan, and Ukraine. Sulfur extracted from oil, gas and the Athabasca Oil Sands has become a glut on the market, with huge stockpiles of sulfur in existence throughout Alberta. Sulfur mined in Alberta, prepared for shipment at Vancouver, B. C. Common naturally occurring sulfur compounds include the metal sulfides, such as pyrite (iron sulfide), cinnabar (mercury sulfide), galena (lead sulfide), sphalerite (zinc sulfide) and stibnite (antimony sulfide); and the metal sulfates, such as gypsum (calcium sulfate), alunite (potassium aluminium sulfate), and barite (barium sulfate). Hydrogen sulfide is the gas responsible for the odor of rotten eggs. It occurs naturally in volcanic emissions, such as from hydrothermal vents, and from bacterial action on decaying sulfurcontaining organic matter. The distinctive colors of Jupiter's volcanic moon, Io, are from various forms of molten, solid and gaseous sulfur. There is also a dark area near the Lunar crater Aristarchus that may be a sulfur deposit. Sulfur is also present in 12 many types of meteorites. Department of Inorganic Chemistry - HUT
Axit yếu Hợp chất S(-II) Dihidro sunfua H2S Khử mạnh Sunfua kim loại 13 Department of Inorganic Chemistry - HUT
H2Sn H2 S n=16 sunfan 14 Department of Inorganic Chemistry - HUT
Mp = - 85.6 oC Bp = - 60.7 oC Kém bền nhiệt so với H2O Bắt đầu phân hủy ở 400 oC 15 Phân hủy hoàn toàn ở 1700 C o Department of Inorganic Chemistry - HUT
H2 S S Tính khử 2 > oxy 2 H 2 S + 3O2 burn −lamnhat 2 SO2 + 2 H 2O 2 H 2 S + O2 Al2O3 < oxy 2S +2 H 2 O Cháy trong oxi Oxi hóa chậm trong KK 2 H 2 S + O2 OXHcham 2S +2 H 2 O 16 Department of Inorganic Chemistry - HUT
ε o I2 / I − = 0.54V ε o H 2 SO3 / S = 0.45V ε o S / H2S = 0.14V H2S + I2 S + 2 HI H 2 SO3 + 2 H 2 S 3S + 3H 2O H 2 S + 4Cl2 + 4 H 2O H 2 SO4 + 8HCl t − phong 5H 2 S + 2 KMnO4 + 3H 2 SO4 2MnSO4 + 5S + K 2 SO4 + 8H 2O 17 Department of Inorganic Chemistry - HUT
H2S HS Tính tan – axit yếu K1 =110−7 + − H 2 S + H 2O ﾈﾈﾈﾈﾈﾈ H 3O + HS ﾈﾈﾈﾈﾈﾈ − K 2 =110−14 + 2− HS + H 2O ﾈﾈﾈﾈﾈﾈﾈ H 3O + S ﾈﾈﾈﾈﾈﾈ S 2 K =3 10−33 + − H 2 S + H 2 S ﾈﾈﾈﾈﾈﾈ H 3 S + HS ﾈﾈﾈﾈﾈﾈ 18 Department of Inorganic Chemistry - HUT
Biological role The amino acids cysteine and methionine contain sulfur, as do all polypeptides, proteins, and enzymes which contain these amino acids. This makes sulfur a necessary component of all living cells. Disulfide bonds between polypeptides are very important in protein assembly and structure. Homocysteine and taurine are also sulfur containing amino acids but are not coded for by DNA nor are they part of the primary structure of proteins. Some forms of bacteria use hydrogen sulfide (H2S) in the place of water as the electron donor in a primitive photosynthesislike process. Sulfur is absorbed by plants via the roots from soil as the sulfate ion and reduced to sulfide before it is incorporated into cysteine and other organic sulfur compounds (sulfur assimilation). Inorganic sulfur forms a part of ironsulfur clusters, and sulfur is the bridging ligand in the CuA site of cytochrome c oxidase. Sulfur 19 is an important component of coenzyme.
FeS +2 HCl = FeCl2 + H 2 S Z > 700o C 3w S + 5w parafin + 2 w amiang H 2 S Z +...... −10o C Na2 S5 + HCl (dac ) H 2 S 2 + H 2 S 3 + H 2 S5 ¨ ¨ H S S H ¨ ¨ ¨ ¨ ¨ S S S ¨ ¨ ¨ t oC H 2 S2 H2S + S Hidro polisunfua 20 Department of Inorganic Chemistry - HUT