Cold vaporized nitrogen can be used to keep materials cool (and in an inert atmosphere) during grinding.. Cryogenic grinding is used in diverse applications, incl[r]
(1)GROUP VA
GROUP VA
Nitrogen Nitrogen NN 77 [He][He]2s2s222p2p33 Phosphorus Phosphorus PP 1515 [Ne][Ne]3s3s223p3p33 Arsenic Arsenic As As 3333 [Ar]3d[Ar]3d10104s4s224p4p33
Antimony Antimony SbSb 5151 [Kr]4d[Kr]4d10105s5s225p5p33 Bismuth Bismuth BiBi 8383 [Rn]4f[Rn]4f14145d5d10106s6s226p6p33
(2)(3)(4)Department of Inorganic Chemistry - HUT ĐẶC ĐIỂM CHUNGĐẶC ĐIỂM CHUNG
NITONITO
Đơn chấtĐơn chất AmoniacAmoniac Oxit nitoOxit nito NitritNitrit
Axit nitricAxit nitric
PHOTPHOPHOTPHO
Đơn chấtĐơn chất
Oxit oxiaxit photphoOxit oxiaxit photpho
(5)(6)(7)PHI KIM GIẢM, KIM LOẠI TĂNG
PHI KIM GIẢM, KIM LOẠI TĂNG
Nitrogen Nitrogen NN 77 [He][He]2s2s222p2p33
Phosphorus Phosphorus PP 1515 [Ne][Ne]3s3s223p3p33
Arsenic Arsenic As As 3333 [Ar]3d[Ar]3d10104s4s224p4p33
Antimony Antimony SbSb 5151 [Kr]4d[Kr]4d10105s5s225p5p33
Bismuth Bismuth BiBi 8383 [Rn]4f[Rn]4f14145d5d10106s6s226p6p33
Department of Inorganic Chemistry - HUT
(8)Khả tạo liên kết
Khả tạo liên kết
• Nito tạo liên kết đơn, kép ba cộng hóa trị.Nito tạo liên kết đơn, kép ba cộng hóa trị.
• Nito nhận 3e tạo hợp chất nitrua với kim loại điển Nito nhận 3e tạo hợp chất nitrua với kim loại điển hình.
hình.
• Các ngun tố cịn lại có AO nd trống nên tạo số OXH Các ngun tố cịn lại có AO nd trống nên tạo số OXH
cao nhất.
cao nhất.
• Nito có khả tạo liên kết cho-nhận Khả tạo Nito có khả tạo liên kết cho-nhận Khả tạo liên kết cho nhận giảm nhanh từ N
liên kết cho nhận giảm nhanh từ N Bi Bi.
ns
ns22npnp33
Số oxi hóa
Số oxi hóa
• Nito có số OXH từ -III đến +V.Nito có số OXH từ -III đến +V.
• Hợp chất quan trọng có số OXH Hợp chất quan trọng có số OXH +III +V, riêng N có số OXH –III.
+III +V, riêng N có số OXH –III.
Qui luật biến đổi
Qui luật biến đổi
• Từ N Từ N P độ bền số OXH +III +V tăng dần có AO nd tham gia P độ bền số OXH +III +V tăng dần có AO nd tham gia
liên kết.
liên kết.
• Từ P Từ P Bi độ bền số OXH +III tăng +V giảm dần tính trơ Bi độ bền số OXH +III tăng cịn +V giảm dần tính trơ
cặp ns tăng dần từ xuống.
cặp ns tăng dần từ xuống.
• Tính KH X(III) giảm dần, tính OXH X(V) tăng dần từ P Tính KH X(III) giảm dần, tính OXH X(V) tăng dần từ P Bi Bi.
(9)Department of Inorganic Chemistry - HUT
ĐẶC ĐIỂM CHUNG
ĐẶC ĐIỂM CHUNG
3( ) 2 ( ) 5( )
3 5
( ) 5 ( )
H
X Cl Cl Cl X Cl
XCl k Cl k XCl k
E E E
X k Cl k
3 5
3 X Cl ( ) 5 X Cl ( ) Cl Cl
H E XCl E XCl E
(10)Department of Inorganic Chemistry - HUT ĐẶC ĐIỂM CHUNGĐẶC ĐIỂM CHUNG
NITONITO
Đơn chấtĐơn chất AmoniacAmoniac Oxit nitoOxit nito NitritNitrit
Axit nitricAxit nitric
PHOTPHOPHOTPHO
Đơn chấtĐơn chất
Oxit oxiaxit photphoOxit oxiaxit photpho
(11)Department of Inorganic Chemistry - HUT
2 *2 2 2 2
( KK ) s s x y z
* 1
(2 2 2 ) 3 2
N
1.095 Å
941 kJ/mol
Mp = - 210 oC
(12)Department of Inorganic Chemistry - HUT
2 p
2s
* s * * x y x y s z N
N NN22 NN
2s
2 p
(13)Department of Inorganic Chemistry - HUT
Nitrogen
Nitrogen (Latin nitrum, Greek Nitron meaning "native soda", "genes", "forming") is formally considered to have been discovered by Daniel Rutherford
in 1772, who called it noxious air or fixed air That there was a fraction of air that did not support combustion was well known to the late 18th century chemist Nitrogen was also studied at about the same time by
Carl Wilhelm Scheele, Henry Cavendish, and Joseph Priestley, who referred to it as burnt air or phlogisticated air Nitrogen gas was inert enough that Antoine Lavoisier referred to it as azote, from the Greek word αζωτος meaning "lifeless" Animals died in it, and it was the principal component of air in which animals had suffocated and flames had burned to extinction This term has become the French word for "nitrogen" and later spread out to many other languages.
Compounds of nitrogen were known in the Middle Ages The alchemists knew nitric acid as aqua fortis (strong water) The mixture of nitric and
hydrochloric acids was known as aqua regia (royal water), celebrated for its ability to dissolve gold (the king of metals) The earliest industrial and
agricultural applications of nitrogen compounds used it in the form of saltpeter ( sodium- or potassium nitrate), notably in gunpowder, and much later, as
(14)Simple compounds
Simple compounds The main neutral hydride of nitrogen is ammonia (NH3), although hydrazine (N2H4) is also commonly used Ammonia is more basic than water by orders of magnitude In solution ammonia forms the ammonium ion (NH4+)
Liquid ammonia (b.p 240 K) is amphiprotic (displaying either Brønsted-Lowry acidic or basic character) and forms ammonium and less commonly) amide ions (NH2-); both
amides and nitride (N3-) salts are known, but decompose in water Singly, doubly, triply
and quadruply substituted alkyl compounds of ammonia are called amines (four substitutions, to form commercially and biologically important quarternary amines, results in a positively charged nitrogen, and thus a water-soluble, or at least amphiphilic, compound) Larger chains, rings and structures of nitrogen hydrides are also known, but are generally unstable.
Other classes of nitrogen anions are azides (N3-), which are linear and isoelectronic to
carbon dioxide Another molecule of the same structure is dinitrogen monoxide (N2O), also known as laughing gas This is one of a variety of oxides, the most prominent of which are nitrogen monoxide (NO) (known more commonly as nitric oxide in biology) and nitrogen dioxide (NO2), which both contain an unpaired electron The latter shows some tendency to dimerize and is an important component of smog.
The more standard oxides, dinitrogen trioxide (N2O3) and dinitrogen pentoxide (N2O5), are actually fairly unstable and explosive The corresponding acids are nitrous (HNO2) and
nitric acid (HNO3), with the corresponding salts called nitrites and nitrates Nitric acid is one of the few acids stronger than hydronium, and is a fairly strong oxidizing agent.
Nitrogen can also be found in organic compounds Common nitrogen functional groups
include: amines, amides, nitro groups, imines, and enamines The amount of nitrogen in a
(15)Nitrogen compounds of notable economic
Nitrogen compounds of notable economic
importance
importance Molecular nitrogen (N2) in the atmosphere is relatively non-reactive due to its strong bond, and N2 plays an inert role in the human body, being neither produced or destroyed In nature, nitrogen is slowly converted into biologically (and industrially) useful compounds by some living organisms, notably certain bacteria (i.e nitrogen fixing bacteria - see Biological role above) Molecular nitrogen is also released into the atmosphere in the process of decay, in dead plant and animal tissues The ability to combine or fix molecular nitrogen is a key feature of modern industrial chemistry, where nitrogen and natural gas are converted into ammonia via the Haber process Ammonia, in turn, can be used directly (primarily as a fertilizer, and in the synthesis of nitrated fertilizers), or as a precursor of many other important materials including explosives, largely via the production of nitric acid by the Ostwald process The salts of nitric acid include important compounds such as potassium nitrate (or saltpeter, important historically for its use in gunpowder) and ammonium nitrate, an important fertilizer and explosive (see ANFO) Various other nitrated organic compounds, such as nitroglycerin and trinitrotoluene, and nitrocellulose, are used as explosives and propellants for modern firearms Nitric acid is used as an oxidizing agent in liquid fueled rockets Hydrazine and hydrazine derivatives find use as rocket fuels In all of these compounds, the basic instability and tendency to burn or explode is derived from the fact that nitrogen is present as an oxide, and not as the far more stable nitrogen molecule (N2) which is a product of the compound's decomposition When nitrates burn or explode, the formation of the powerful triple bond in the N2 which results, produces most of the energy of the reaction
Nitrogen is a constituent of molecules in every major drug class in pharmacology and medicine
Nitrous oxide (N20) was discovered early in the 19th century to be a partial anesthetic, though it was not used as a surgical anesthetic until later Called "laughing gas", it was found capable of inducing a state of social disinhibition resembling drunkenness Other notable nitrogen-containing drugs are drugs derived from plant alkaloids, such as morphine (there exist many alkaloids known to have pharmacological effects; in some cases they appear natural chemical defences of plants against predation) Nitrogen containing drugs include all of the major classes of antibiotics, and organic nitrate drugs like nitroglycerin and
(16)Department of Inorganic Chemistry - HUT
Multi-Industry Uses:
Multi-Industry Uses:
The inert properties of nitrogen make it a good blanketing gas in many applications Nitrogen blanketing is used to protect flammable or explosive solids and liquids from contact with air Certain chemicals, surfaces of solids, and stored food products have properties that must be protected from degradation by the effects of atmospheric oxygen and moisture Protection is achieved by keeping these items in (under) a nitrogen atmosphere "Inerting" or "padding" are other terms used to describe displacement of air and nitrogen blanketing.
"Sparging" with nitrogen is the bubbling of nitrogen through a liquid to remove unwanted volatile components, including volatile organic compounds (VOC) which may be necessary to meet pollution reduction regulations.
Certain substances are difficult to pulverize or shred because they are tough or the materials will be degraded by the heat generated by mechanical processes such as grinding Liquid nitrogen can be used to freeze soft or tough substances prior to their entering a size reduction process Cold vaporized nitrogen can be used to keep materials cool (and in an inert atmosphere) during grinding Cryogenic grinding is used in diverse applications, including production of finely ground pharmaceuticals, plastics and pigments; and for shredding tires in recycling plants
(17)Metals:
Nitrogen is used to treat the melt in the manufacture of steel and other metals and as a shield gas in the heat treatment of iron, steel and other metals It is also used as a process gas, together with other gases for reduction of carbonization and nitriding.
“Flash” or “fins” on cast metal can be removed by cooling with liquid nitrogen, making them brittle, allowing then to be broken off by mechanical action
Manufacturing and Construction:
Shrink fitting is an interesting alternative to traditional expansion fitting Instead of heating the outer metal part, the inner part is cooled by liquid nitrogen so that the metal shrinks and can be inserted When the metal returns to its normal temperature, it expands to its original size, giving a very tight fit.
(18)Chemicals, Pharmaceuticals and Petroleum:
Refineries, petrochemical plants and marine tankers use nitrogen to purge equipment, tanks and pipelines of dangerous vapors and gases (for example, after completing a pipeline transfer operation or ending a production run) and to maintain an inert and protective atmosphere in tanks storing flammable liquids
Cold nitrogen gas is used to cool reactors filled with catalyst during maintenance work The cooling time can be reduced substantially
Cooling reactors (and the materials inside) to low temperature allows better control of side-reactions in complex reactions in the pharmaceutical industry Liquid nitrogen is often used to provide the necessary refrigeration as it can produce rapid temperature reduction and easily maintain the required cold reaction temperatures Reactor cooling and temperature control systems usually employ a circulating low-temperature heat transfer fluid to transfer refrigeration produced by vaporizing liquid nitrogen to the shell of the reactor vessel The liquid nitrogen is vaporized in specially-designed heat exchangers that transfer refrigeration to the circulating heat transfer fluid Liquid nitrogen is used during well completion to "frac" natural gas bearing rock formations, in particular, tight gas formations, including shale gas and natural gas from coal (coal bed methane) where water based methods should be avoided Nitrogen is also used to maintain pressure in oil and natural gas producing formations Unlike carbon dioxide, which is also used for pressurization, nitrogen has little affinity for liquid hydrocarbons, thus it builds up in and remains in the gas cap Nitrogen is used an inert gas to push liquids though lines, to clear lines and to propel "pigs" through pipelines to sweep out one material before using the line to transport another material
Rubber and Plastics:
(19)Food and Beverages:
The intense cold in liquid nitrogen allows very rapid freezing of food items, resulting in minimal cell damage from ice crystals and improved appearance, taste and texture Well-designed cryogenic tunnel and spiral freezers efficiently capture refrigeration from liquid vaporization and from the cold nitrogen gas as it flows through the freezer
When substances such as vegetable oil and wines are stored, the inert properties of nitrogen can be used to protect against loss of quality by oxidation by expelling any air entrained in the liquid (“sparging”) and protecting liquids in storage tanks by filling the vapor space (“blanketing”)
Nitrogen (and nitrogen mixed with CO2 and oxygen) is used in transport trucks and in Modified Atmosphere Packaging (MAP) to extend the shelf life of packaged foods by preventing oxidation, mold, insect infestation and moisture migration
Health Care:
Nitrogen is used as a shield gas in the packing of some medicines to prevent degradation by oxidation or moisture adsorption
Nitrogen is used to freeze blood, as well as viruses for vaccination It is also used to freeze livestock semen, which can then be stored for years The quick freezing resulting from the intense cold minimizes cell wall damage Liquid nitrogen is also used in some MRI (Magnetic Resonance Imaging) devices to pre-cool the low temperature magnets prior to using much more expensive liquid helium for final cooling
Liquid nitrogen is used in cryo-surgery to destroy diseased tissue
Miscellaneous:
(20)Department of Inorganic Chemistry - HUT
4 2 2 2 2
o
t C
NH NO N H O
3 2
(21)Distillation
(22)Department of Inorganic Chemistry - HUT
2 p
2s
* s * * x y x y s z
1sa
1sb
1sc
N
(23)Mp = - 78 oC
Bp = - 33 oC
Tồn liên kết hidro
(24)(25)Department of Inorganic Chemistry - HUT
Bazo Khử
(26)Department of Inorganic Chemistry - HUT
5 1.8 10
3( ) 3. 4
b
K
NH k aq NH aq NH OH
2
2
3 3 4
4NH Cu Cu NH( )
180 ,140 2
o
atm C
CO NH O C
2 NH O C ONH 2 NH H O NH
(27)(28)Department of Inorganic Chemistry - HUT
3 2 2 2
4NH 3O chay 2N 6H O
,800
3 2 2
4NH 5O Pt o C 4NO 6H O
3 2 2 4
(29)Department of Inorganic Chemistry - HUT
400
3 2 2
2NH 2Na o C 2NaNH H
800 900
3 2
2NH 2 Al o C 2 AlN 3H
amidua
(30)Because of its many uses, ammonia is one of the most highly-produced inorganic chemicals There are dozens of chemical plants worldwide that produce ammonia The worldwide ammonia production in 2004 was 109 million metric tonnes.[6] the
People's Republic of China produced 28.4% of the worldwide production followed by India with 8.6%, Russia with 8.4%, and the
United States with 8.2%.[6] About 80% or more of the ammonia produced is used for fertilizing agricultural crops.[6]
Before the start of World War I most ammonia was obtained by the dry distillation[7] of nitrogenous vegetable and animal waste products, including cameldung where it was distilled[5] by the reduction of nitrous acid and nitrites with hydrogen; additionally, it was produced by the distillation of coal;[5] and also by the decomposition of ammonium salts by alkaline hydroxides[8] or by quicklime, the salt most generally used being the chloride (sal-ammoniac) thus:
2 NH4Cl + CaO → CaCl2 + Ca(OH)2 + NH3
Today, the typical modern ammonia-producing plant first converts natural gas (i.e methane) or liquified petroleum gas (such gases are propane and butane) or petroleum naphtha into gaseous hydrogen Starting with a natural gas feedstock, the processes used in producing the hydrogen are:
The first step in the process is to remove sulfur compounds from the feedstock because sulfur deactivates the catalysts used in subsequent steps Sulfur removal requires catalytic hydrogenation to convert sulfur compounds in the feedstocks to gaseous
hydrogen sulfide:
H2 + RSH → RH + H2S(g)
The gaseous hydrogen sulfide is then absorbed and removed by passing it through beds of zinc oxide where it is converted to solid
zinc sulfide:
H2S + ZnO → ZnS + H2O
Catalytic steam reforming of the sulfur-free feedstock is then used to form hydrogen plus carbon monoxide: CH4 + H2O → CO + H2
The next step then uses catalytic shift conversion to convert the carbon monoxide to carbon dioxide and more hydrogen: CO + H2O → CO2 + H2
The carbon dioxide is then removed either by absorption in aqueous ethanolamine solutions or by adsorption in
pressure swing adsorbers (PSA) using proprietary solid adsorption media
The final step in producing the hydrogen is to use catalytic methanation to remove any small residual amounts of carbon monoxide or carbon dioxide from the hydrogen:
CO + H2 → CH4 + H2O CO2 + H2 → CH4 + H2O
To produce the desired end-product ammonia, the hydrogen is then catalytically reacted with nitrogen (derived from process air) to form anhydrous liquid ammonia This step is known as the ammonia synthesis loop (also referred to as the Haber-Bosch process):
3 H2 + N2 → NH3
(31)Department of Inorganic Chemistry - HUT
2
380 450 ,220
2 2 1% , 3% , , 3
1 3
( ) ( ) ( )
2 2
oC atm
Fe K O CaO Al O SiO MgO
N k H k NH k
298 298 46.19 16.63 o o H kJ G kJ 2 2
2 3 ( , , / )
C f T P k N H
Hiệu suất chuyển hóa ~ 17 %
(32)Haber Process
(33)(34)The most important single use of ammonia is in the production of nitric acid A mixture of one part ammonia to nine parts air is passed over a platinum gauze catalyst at 850 °C, whereupon the ammonia is oxidized to nitric oxide
4 NH3 + O2 → NO + H2O
The catalyst is essential, as the normal oxidation (or combustion) of ammonia gives dinitrogen and water: the production of nitric oxide is an example of kinetic control As the gas mixture cools to 200–250 °C, the nitric oxide is in turn oxidized by the excess of oxygen present in the mixture, to give nitrogen dioxide This is reacted with water to give nitric acid for use in the production of
fertilizers and explosives
In addition to serving as a fertilizer ingredient, ammonia can also be used directly as a fertilizer by forming a solution with irrigation water, without additional chemical processing This later use allows the continuous growing of nitrogen dependent crops such as maize (corn) without crop rotation but this type of use leads to poor soil health
Ammonia has thermodynamic properties that make it very well suited as a refrigerant, since it liquefies readily under pressure, and was used in virtually all refrigeration units prior to the advent of haloalkanes such as Freon However, ammonia is a toxic irritant and its corrosiveness to any
copper alloys increases the risk that an undesirable leak may develop and cause a noxious hazard Its use in small refrigeration units has been largely replaced by haloalkanes, which are not toxic irritants and are practically not flammable Ammonia continues to be used as a refrigerant in large industrial processes such as bulk icemaking and industrial food processing Ammonia is also useful as a component in absorption-type refrigerators, which not use compression and expansion cycles but can exploit heat differences Since the implication of haloalkane being major contributors to ozone depletion, ammonia is again seeing increasing use as a refrigerant
It is also sometimes added to drinking water along with chlorine to form chloramine, a disinfectant Unlike chlorine on its own, chloramine does not combine with organic (carbon containing) materials to form carcinogenic halomethanes such as chloroform
(35)Department of Inorganic Chemistry - HUT
2 3 2
(36)(37)(38)Department of Inorganic Chemistry - HUT
0.94
3 2 3 2 2
o V
NO e H HNO H O
1.00
2 2
o V
HNO e H NO H O
2
2 4 3 2
5NO 2MnO 6H 5NO 2Mn 3H O
2 2 2
2NO 2I 4H 2NO I 2H O
Tính chất khử
Tính chất khử
Tính chất oxi hóa
(39)(40)In inorganic chemistry, nitrites are salts of nitrous acid HNO2 They contain the nitrite ion NO2− Nitrites of the alkali and alkaline earth metals can be
synthesized by reacting a mixture of nitrogen monoxide NO and
nitrogen dioxide NO2 with the corresponding metal hydroxide solution, as well as through the thermal decomposition of the corresponding nitrate Other
nitrites are available through the reduction of the corresponding nitrates.
Sodium nitrite is used for the curing of meat because it prevents bacterial growth and, in a reaction with the meat's myoglobin, gives the product a desirable dark red color Because of the toxicity of nitrite (lethal dose of nitrite
for humans is about 22 mg per kg body weight), the maximum allowed nitrite concentration in meat products is 200 ppm Under certain conditions, especially
during cooking, nitrites in meat can react with degradation products of
amino acids, forming nitrosamines, which are known carcinogens.
In organic chemistry, nitrites mean the esters of nitrous acid They possess the general formula R-O-N=O, R being an aryl or alkyl group Amyl nitrite is used in
medicine for the treatment of heart diseases.
Nitrites should not be confused with nitrates, the salts of nitric acid, or with
nitro compounds, though they share the formula NO2 The nitrite ion NO2− should not be confused with the nitronium ion NO2+.
Nitrite is detected and analyzed by the Griess Reaction, involving the formation of a deeply red-color azo dye upon treatment of a NO2−-containing
(41)Department of Inorganic Chemistry - HUT
298 298
2 4 H o 57.2kJ G; o 4.77kJ 2 2
N O NO
(42)(43)(44)(45)(46)Commonly used as a laboratory reagent, nitric acid is used in the manufacture of explosives such as nitroglycerin, trinitrotoluene (TNT) and
Cyclotrimethylenetrinitramine (RDX), as well as fertilizers such as
ammonium nitrate.
Also, in ICP-MS and ICP-AES techniques, nitric acid (with a concetration from 0.5% to 1.5%) is used as a matrix compound for determining metal traces in solutions An ultrapure acid is needed for such determination, because any small amount of metal ions could affect the result of the analysis.
It has additional uses in metallurgy and refining as it reacts with most metals, and in organic syntheses When combined with hydrochloric acid, it forms
aqua regia, one of the few reagents capable of dissolving gold and platinum. Nitric acid is also a component of acid rain.
Nitric acid is a very powerful oxidizing agent, and the reactions of nitric acid with compounds such as cyanides, carbides, and metallic powders can be
explosive Reactions of nitric acid with many organic compounds, such as
turpentine, are violent and hypergolic (i.e., self-igniting).
Concentrated nitric acid dyes human skin yellow on contact, due to interactions with the skin protein keratin Yet these yellow stains turn orange when
alkalised.
One use for IWFNA is as an oxidizer in liquid fuel rockets.
(47)Department of Inorganic Chemistry - HUT ĐẶC ĐIỂM CHUNGĐẶC ĐIỂM CHUNG
NITONITO
Đơn chấtĐơn chất AmoniacAmoniac Oxit nitoOxit nito NitritNitrit
Axit nitricAxit nitric
PHOTPHOPHOTPHO
Đơn chấtĐơn chất
Oxit oxiaxit photphoOxit oxiaxit photpho
(48)P
P∞∞
Mp ~ 600
Mp ~ 600 ooCC
P
P44
Mp ~ 44.2
Mp ~ 44.2 ooCC
800 3000
, , 270 48 4,
o o o
C C
black red C h liquid
P P P P P P
(49)Ít bền
Ít bền
Oxi hóa chậm phát
Oxi hóa chậm phát
lân quang
lân quang
Bốc cháy 35
Bốc cháy 35 ooC C
bảo quản bảo quản
khí trơ nước
(50)(51)2 4 10
2 4 6
2 5 2 3
oxy oxy
P O P O P O P O
Tính oxi hóa
Tính oxi hóa
3 2
2P 3Ca Ca P
3 4 4 2 3 4
2Ca PO( ) 6SiO 10C 6CaSiO 10CO P
(52)Concentrated phosphoric acids, which can consist of 70% to 75% P2O5 are very important to agriculture and farm production in the form of fertilizers Global demand for fertilizers led to large increases in phosphate (PO43-) production in the second half of the 20th century Other uses;
Phosphates are utilized in the making of special glasses that are used for sodium lamps Bone-ash, calcium phosphate, is used in the production of fine china
Sodium tripolyphosphate made from phosphoric acid is used in laundry detergents in several countries, and banned for this use in others
Phosphoric acid made from elementary phosphorus is used in food applications such as soda beverages The acid is also a starting point to make food grade phosphates[4] These include mono-calcium phosphate which is employed in baking powder and sodium tripolyphosphate and other sodium phosphates[4] Among other uses, these are used to improve the characteristics of processed meat and cheese Others are used in toothpaste[4] Trisodium phosphate is used in cleaning agents to soften water and for preventing pipe/boiler tube corrosion
Phosphorus is widely used to make organophosphorus compounds, through the intermediates phosphorus chlorides and the two phosphorus sulfides: phosphorus pentasulfide, and
phosphorus sesquisulfide.[4] Organophosphorus compounds have many applications, including in
plasticizers, flame retardants, pesticides, extraction agents, and water treatment Phosphorus sesquisulfide is used in heads of strike-anywhere matches[4]
This element is also an important component in steel production, in the making of phosphor bronze, and in many other related products
White phosphorus is used in military applications as incendiary bombs, for smoke-screening as smoke pots and smoke bombs, and in tracer ammunition
Red phosphorus is essential for manufacturing matchbook strikers, flares,[4] and, most notoriously, methamphetamine
In trace amounts, phosphorus is used as a dopant for N-type semiconductors
(53)Department of Inorganic Chemistry - HUT P
P
P
P44OO1010 H H33POPO44
P
P44SS33, P, P44SS1010
PCl
PCl33, PCl, PCl55, POCl, POCl33
Thuốc trừ sâu
(54)Department of Inorganic Chemistry - HUT
4 10 2 3
4
2 ( )n
P O H O HPO
n
4 10 4 2 2 4 2 7
P O H O H P O
4 10 6 2 4 3 4
P O H O H P O
Axit metaphotphoric
Axit metaphotphoric
Axit diphotphoric
Axit diphotphoric
Axit orthophotphoric
(55)(56)Department of Inorganic Chemistry - HUT
2
2
,260 ,300
3 4 4 2 7 3
2 nH O oC nH O oC 2( )n
nH O nH O
nH PO nH P O HPO
(57)There are two distinct kinds of phosphoric acid:
Thermal phosphoric acid: This very pure phosphoric acid is obtained by burning elemental phosphorus to produce phosphorus pentoxide and dissolving the product in dilute phosphoric acid This is the cleanest way of producing phosphoric acid, since most impurities present in the rock have been removed when extracting Phosphorus from the rock in a furnace The end result is food grade, thermal phosphoric acid; however, for critical applications additional processing to remove arsenic compunds may be needed.
Wet phosphoric acid: Green phosphoric acid is prepared by adding sulfuric acid to calcium phosphate rock While phosphoric acid has the potential to release three hydrogen ions, in aqueous solution the third requires a high pH because PO43− is almost as strong a base as hydroxide ion.
Through modern filtering techniques the wet process acid can be cleaned up significantly but still isn't as pure as thermal phosphoric acid; as it may contain other acidic species such as hydrofluoric acid.
4 10 6 2 4 3 4
P O H O H P O 80
5 ( 3) 5 10 5 4.2 3
oC
(58)Department of Inorganic Chemistry - HUT ĐẶC ĐIỂM CHUNGĐẶC ĐIỂM CHUNG
NITONITO
Đơn chấtĐơn chất AmoniacAmoniac Oxit nitoOxit nito NitritNitrit
Axit nitricAxit nitric
PHOTPHOPHOTPHO
Đơn chấtĐơn chất
Oxit oxiaxit photphoOxit oxiaxit photpho
(59)Department of Inorganic Chemistry - HUT
4 6 4 6 2 3
As O Sb O Bi O
2 3 2 3
FeAsS pirit asen Sb S antimonit
Bi S bimutin
, ,
C
Oxide As Sb Bi 1.
1. Sb khơng khí nhiệt độ thường khơng biến đổi.Sb khơng khí nhiệt độ thường khơng biến đổi. 2.
2. As, Bi bị oxi hóa bề mặt.As, Bi bị oxi hóa bề mặt. 3.
3. Khi đun nóng, tạo oxit với số OXH +III.Khi đun nóng, tạo oxit với số OXH +III. 4.
4. Ở dạng bột mịn cháy khí Clo nhiệt Ở dạng bột mịn cháy khí Clo nhiệt độ thường tạo triclorua XCl
độ thường tạo triclorua XCl33.. 5.
5. Khi đun nóng phản ứng với Br, I, S số kim Khi đun nóng phản ứng với Br, I, S số kim loại.
loại.
(60)Department of Inorganic Chemistry - HUT
3 2 3 4
3As 5HNO 2H O 3H AsO 5NO
3 2 2 5 2
3Sb 10HNO (x 5)H O 3Sb O xH O. 10NO
3 3 3 2
4 ( ) 2
Bi HNO Bi NO NO H O
1.
1.Không tác dụng với nước.Không tác dụng với nước.
2.
2.Không đẩy hidro khỏi axit.Không đẩy hidro khỏi axit.
1.
1.Tính bền số OXH +V giảm dần Tính bền số OXH +V giảm dần tính OXH tăng dần tính OXH tăng dần
2.
(61)Department of Inorganic Chemistry - HUT
3 2 3 2
( ) 3 2 3
Bi OH Cl NaOH NaBiO NaCl H O
2
3
5KBiO r( ) 2Mn 14H Bi 2MnO 5K 7H O
3 4 2 2 3 3 2 2
H AsO I H H AsO I H O
Bi3+ có tính khử yếu tạo Bi5+ với chất OXH mạnh
trong môi trường kiềm mạnh đặc.
Bi5+ có tính oxi hóa mạnh
Tính OXH trung bình mơi trường axit
(62)(63)Department of Inorganic Chemistry - HUT
2 5 3 2 2 3 4
As O H O H AsO
4 6 6 2 4 3 3 4 2 4 2
As O H O H AsO H O HAsO
3
3
3 ( ) ( )
X OH X OH XO OH
Axit asenic
(64)(65)Department of Inorganic Chemistry - HUT
3 2 2
SbCl H O SbOCl HCl
3 3 2 3 3
( ) 2
Bi NO H O BiONO HNO
Antimonyl clorua
Antimonyl clorua
Bitmutyl nitrate
(66)Department of Inorganic Chemistry - HUT
BÀI TẬP
BÀI TẬP
Thứ 5: 1-3-2007
Thứ 5: 1-3-2007
Bài: đến 6
Bài: đến 6
Chương 2: Hidro &
Chương 2: Hidro &
Halogen
Latin Greek Daniel Rutherford 1772 combustion Carl Wilhelm Scheele Henry Cavendish Joseph Priestley inert Antoine Lavoisier French Middle Ages. alchemists nitric acid hydrochloric acids gold agricultural saltpeter sodium- potassium nitrate) gunpowder, fertilizer, feedstock hydride ammonia H hydrazine basic water solution ammonium ion amphiprotic Brønsted-Lowry amide nitride salts decompose amines amphiphilic, 2O electron of smog dinitrogen trioxide dinitrogen pentoxide nitrous nitrites nitrates hydronium oxidizing agent. functional groups e: amines, amides, nitro imines, enamines chemical substance can be Kjeldahl method. bacteria nitrogen fixing bacteria natural gas Haber process explosives Ostwald process ammonium nitrate ANFO) nitroglycerin trinitrotoluene nitrocellulose rockets. fuels Nitrous oxide laughing gas alkaloids morphine nitroprusside nitric oxide ammonia production metric tonnes. People's Republic of China India Russia United States World War I ry distillation camel dung coal alkaline quicklime sal-ammoniac) methane) liquified petroleum gas propane butane) naphtha sulfur catalysts hydrogenation hydrogen sulfide zinc oxide zinc sulfide: c steam reforming carbon monoxide shift conversion carbon dioxide ethanolamine y adsorption pressure swing adsorbers Haber-Bosch bar Haldor Topsoe Denmark, Lurgi AG Germany, Kellogg, Brown and Root platinum dinitrogen kinetic control nitrogen dioxide. explosives maize soil refrigerant, haloalkanes Freon copper alloys flammable. refrigerant absorption-type refrigerators, o ozone depletion chlorine chloramine disinfectant. carcinogenic halomethanes chloroform Tobacco cigarettes nicotine inorganic chemistry, alkali alkaline earth metals nitrogen monoxide hydroxide reduction Sodium nitrite curing of meat myoglobin ppm amino acids nitrosamines organic chemistry esters aryl alkyl Amyl nitrite nitro compounds nitronium ion sulfanilic acid reagent, Cyclotrimethylenetrinitramine ICP-MS ICP-AES metallurgy refining metals organic syntheses aqua regia acid rain cyanides carbides turpentine hypergolic skin protein keratin oxidizer liquid fuel rockets phosphoric acids, phosphate e 20th century glasses sodium lamps calcium phosphate fine china Sodium tripolyphosphate baking powder Trisodium phosphate soften water corrosion organophosphorus compounds, phosphorus chlorides phosphorus pentasulfide, phosphorus sesquisulfide. plasticizers flame retardants pesticides extraction agents matches steel phosphor bronze, White phosphorus military incendiary bombs, smoke-screening nd smoke bombs n tracer ammunition