group va group va nitrogen n 7 he2s22p3 phosphorus p 15 ne3s23p3 arsenic as 33 ar3d104s24p3 antimony sb 51 kr4d105s25p3 bismuth bi 83 rn4f145d106s26p3 department of inorganic chemistry hut d

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

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

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

• 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.

• 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

• 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

• 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.

• 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.

• 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)

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)

 NITONITO

(11)

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)

2 p     

2s    

* s      * * x y     x y         s      z      N

N NN22 NN

2s

   

2 p

(13)

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

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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

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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

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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

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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.

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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:

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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)

4 2 2 2 2

o

t C

NH NO   N  H O

3 2

(21)

Distillation

(22)

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)

Bazo Khử

(26)

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)

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)

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)

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)

2 3 2

(36)

(37)

(38)

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 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)

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)

 NITONITO

(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

Oxi hóa chậm phát

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

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

P44OO1010  H H33POPO44

P

P44SS33, P, P44SS1010

PCl

PCl33, PCl, PCl55, POCl, POCl33

Thuốc trừ sâu

(54)

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 diphotphoric

Axit orthophotphoric

(55)

(56)

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)

 NITONITO

(59)

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)

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)

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)

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 ( ) ( )

X  OH  X OH XO OH

     

Axit asenic

(64)

(65)

3 2 2

SbCl  H O    SbOCl   HCl

3 3 2 3 3

( ) 2

Bi NO  H O    BiONO   HNO

Antimonyl clorua

Bitmutyl nitrate

(66)

BÀI TẬP

Thứ 5: 1-3-2007

Bài: đến 6

Chương 2: Hidro &

Halogen

group va group va nitrogen n 7 he2s22p3 phosphorus p 15 ne3s23p3 arsenic as 33 ar3d104s24p3 antimony sb 51 kr4d105s25p3 bismuth bi 83 rn4f145d106s26p3 department of inorganic chemistry hut d

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