Chuong 4-Calcogens-2

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Department of Inorganic Chemistry - HUT
GROUP VIA
Oxygen Family - Calcogens
Đặc điểm chung
Oxygen
Tính chất lý học
Tính chất hóa học
Vai trò sinh học
Trạng thái tự nhiên, điều chế và ứng dụng
Ozon
Oxide
Hydroxide
Hydro peoxide
Lưu huỳnh
Đơn chất
Hợp chất S(-II)
Hợp chất S(IV)
Hợp chất S(VI)
Một số hợp chất khác của lưu huỳnh
Oxygen O
Sulfur S
Selenium Se
Tellurium Te
Polonium Po
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Department of Inorganic Chemistry - HUT
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Department of Inorganic Chemistry - HUT
Sulfur – S
[Ne]3s23p4
Sulfur is a non-metallic 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 grain.
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rhombic
hệ trực thoi
monoclinic
hệ một nghiêng
monoclinic
hệ một nghiêng
R
R
160 oC, nhớt
200 oC, đặc quánh
440 oC, linh động
Hơi
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Department of Inorganic Chemistry - HUT
Màu vàng
d=2.06 g/cm3
Mp=112.8 oC
Vàng nhạt
d=1.96 g/cm3
Mp=119.2 oC
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Department of Inorganic Chemistry - HUT
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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.
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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.
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Department of Inorganic Chemistry - HUT
Tính chất hóa học:
Tính vừa oxi hóa vừa khử: tan trong kiềm đặc, kiềm nóng chảy, sunfua, sunfit.
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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 light-generating 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, the craft of sulfur inlays was soon abandoned.
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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 "pest-averting 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 mining operations. Therefore the Frasch process was utilized
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Department of Inorganic Chemistry - HUT
OCCURRENCE
Sulfur
Sulfur crystalites at Wai-o-tapu 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 sulfur-containing 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 many types of meteorites.
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Department of Inorganic Chemistry - HUT
Hợp chất S(-II)
Dihidro sunfua
H2S
Sunfua kim loại
Axit yếu
Khử mạnh
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Department of Inorganic Chemistry - HUT
H2Sn
H2S
n=1-6
sunfan
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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
Phân hủy hoàn toàn ở 1700 oC
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Department of Inorganic Chemistry - HUT
H2S
S2-
Tính khử
Cháy trong oxiOxi hóa chậm trong KK
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Department of Inorganic Chemistry - HUT
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Department of Inorganic Chemistry - HUT
H2S
Tính tan – axit yếu
HS-
S2-
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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 photosynthesis-like 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 iron-sulfur clusters, and sulfur is the bridging ligand in the CuA site of cytochrome c oxidase. Sulfur is an important component of coenzyme.
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Department of Inorganic Chemistry - HUT
Hidro polisunfua
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Department of Inorganic Chemistry - HUT
Sunfua kim loại
Muối của axit sunfuhidric H2S là:
hidro sunfua HS-
sunfua S2-
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Department of Inorganic Chemistry - HUT
Sunfua
Tan trong nước
Không tan trong nước
Tan trong axit loãng
Không tan trong nước
Không tan trong axit loãng
Dùng T để phát hiện ion kim loại trong Hóa phân tích
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Department of Inorganic Chemistry - HUT
Điều chế
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Department of Inorganic Chemistry - HUT
Mp= - 72.7 oC
Bp = - 10 oC
Hợp chất S(+IV)
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Department of Inorganic Chemistry - HUT
Tính tan
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Department of Inorganic Chemistry - HUT
SO2
S4+
Tính oxi hóa yếu
S4+ có thể bị oxi hóa trong cả môi trường axit, trung tính và bazo
Tính khử mạnh
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Department of Inorganic Chemistry - HUT
Tính khử mạnh
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Department of Inorganic Chemistry - HUT
Tính oxi hóa yếu
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Department of Inorganic Chemistry - HUT
Hợp chất S(+VI)
SO3
S6+
Mp = 10.37 oC
Bp = 280 oC
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Department of Inorganic Chemistry - HUT
Axít mạnh
Oxi hóa
Sunfo hóa
Hidrat hóa
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Department of Inorganic Chemistry - HUT
Axít mạnh
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Department of Inorganic Chemistry - HUT
Một số phi kim như P, S, C bị oxi hóa đến oxit hoặc axit tương ứng
Oxi hóa
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Department of Inorganic Chemistry - HUT
Sunfo hóa
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Department of Inorganic Chemistry - HUT
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Department of Inorganic Chemistry - HUT
Phương pháp tiếp xúc
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Department of Inorganic Chemistry - HUT
Environmental impact
The burning of coal and petroleum by industry and power plants liberates huge amounts of sulfur dioxide (SO2) which reacts with atmospheric water and oxygen to produce sulfuric acid. This sulfuric acid is a component of acid rain, which lowers the pH of soil and freshwater bodies, resulting in substantial damage to the natural environment and chemical weathering of statues and architecture. Fuel standards increasingly require sulfur to be extracted from fossil fuels to prevent the formation of acid rain. This extracted sulfur is then refined and represents a large portion of sulfur production.
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Department of Inorganic Chemistry - HUT
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Department of Inorganic Chemistry - HUT
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Department of Inorganic Chemistry - HUT
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Department of Inorganic Chemistry - HUT
Một số hợp chất khác của lưu huỳnh
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Department of Inorganic Chemistry - HUT
Có tính oxi hóa rất mạnh
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Department of Inorganic Chemistry - HUT
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Department of Inorganic Chemistry - HUT
Tính khử
Tạo phức
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Department of Inorganic Chemistry - HUT
Iodometry
Loại vết Cl còn lại sau khi tẩy trắng sợi và giấy
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Department of Inorganic Chemistry - HUT
Sir John Frederick William Herschel
7 March 1792 – 11 May 1871
Photography: làm thuốc định hình do hòa tan AgBr, AgCl tạo phức chất
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Department of Inorganic Chemistry - HUT
Compounds
Hydrogen sulfide has the characteristic smell of rotten eggs. Dissolved in water, hydrogen sulfide is acidic and will react with metals to form a series of metal sulfides. Natural metal sulfides are common, especially those of iron. Iron sulfide is called pyrite, the so called fool`s gold. Interestingly, pyrite can show semiconductor properties.[1] Galena, a naturally occurring lead sulfide, was the first semiconductor discovered, and found a use as a signal rectifier in the "cat`s whiskers" of early crystal radios.
Many of the unpleasant odors of organic matter are based on sulfur-containing compounds such as methyl and ethyl mercaptan used to scent natural gas so that leaks are easily detectable. The odor of garlic and "skunk stink" are also caused by sulfur-containing organic compounds. However, not all organic sulfur compounds smell unpleasant; for example, grapefruit mercaptan, a sulfur-containing monoterpenoid is responsible for the characteristic scent of grapefruit.
Polymeric sulfur nitride has metallic properties even though it does not contain any metal atoms. This compound also has unusual electrical and optical properties. This polymer can be made from tetrasulfur tetranitride S4N4.
Phosphorus sulfides are important in synthesis. For example, P4S10 and its derivatives Lawesson`s reagent and naphthalen-1,8-diyl 1,3,2,4-dithiadiphosphetane 2,4-disulfide are used to replace oxygen from some organic molecules with sulfur.
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Department of Inorganic Chemistry - HUT
Inorganic sulfur compounds:
Sulfides (S2−), a complex family of compounds usually derived from S2−. Cadmium sulfide (CdS) is an example.
Sulfites (SO32−), the salts of sulfurous acid (H2SO3) which is generated by dissolving SO2 in water. Sulfurous acid and the corresponding sulfites are fairly strong reducing agents. Other compounds derived from SO2 include the pyrosulfite or metabisulfite ion (S2O52−).
Sulfates (SO42−), the salts of sulfuric acid. Sulfuric acid also reacts with SO3 in equimolar ratios to form pyrosulfuric acid (H2S2O7).
Thiosulfates (sometimes referred to as thiosulfites or "hyposulfites") (S2O32−). Thiosulfates are used in photographic fixing (HYPO) as reducing agents. Ammonium thiosulfate is being investigated as a cyanide replacement in leaching gold.[2]
Sodium dithionite, Na2S2O4, is the highly reducing dianion derived from hyposulfurous/dithionous acid.
Sodium dithionate (Na2S2O6).
Polythionic acids (H2SnO6), where n can range from 3 to 80.
Peroxymonosulfuric acid (H2SO5) and peroxydisulfuric acids (H2S2O8), made from the action of SO3 on concentrated H2O2, and H2SO4 on concentrated H2O2 respectively.
Sodium polysulfides (Na2Sx)
Sulfur hexafluoride, SF6, a dense gas at ambient conditions, is used as nonreactive and nontoxic propellant
Sulfur nitrides are chain and cyclic compounds containing only S and N. Tetrasulfur tetranitride S4N4 is an example.
Thiocyanates contain the SCN− group. Oxidation of thiocyanoate gives thiocyanogen, (SCN)2 with the connectivity NCS-SCN.
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Department of Inorganic Chemistry - HUT
Selenium, Tellurium, and Polonium
Selenium increases conductivity in the presence of light.
Used in light meters, cameras,photocopiers.
Used in rectifiers to converts AC current to DC.
Used to give red color to glass.
Tellurium is a metalloid used in semiconductors.
Polonium is radioactive.