Chuong 5-Group VA

GROUP VA
Nitrogen N 7 [He]2s22p3
Phosphorus P 15 [Ne]3s23p3
Arsenic As 33 [Ar]3d104s24p3
Antimony Sb 51 [Kr]4d105s25p3
Bismuth Bi 83 [Rn]4f145d106s26p3
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
ĐẶC ĐIỂM CHUNG
NITO
Đơn chất
Amoniac
Oxit của nito
Nitrit
Axit nitric
PHOTPHO
Đơn chất
Oxit và oxiaxit của photpho
ASEN, ANTIMON, BITMUS
Department of Inorganic Chemistry - HUT
PHI KIM GIẢM, KIM LOẠI TĂNG
Nitrogen N 7 [He]2s22p3
Phosphorus P 15 [Ne]3s23p3
Arsenic As 33 [Ar]3d104s24p3
Antimony Sb 51 [Kr]4d105s25p3
Bismuth Bi 83 [Rn]4f145d106s26p3
Department of Inorganic Chemistry - HUT
+III
+V
+V
III+
Khả năng tạo liên kết
Nito tạo liên kết đơn, kép hoặc ba cộng hóa trị.
Nito nhận 3e tạo hợp chất nitrua với kim loại điển hình.
Các nguyên tố còn lại có AO nd trống nên tạo số OXH cao nhất.
Nito có khả năng tạo liên kết cho-nhận. Khả năng tạo liên kết cho nhận giảm nhanh từ N  Bi.
ns2np3
Số oxi hóa
Nito có số OXH từ -III đến +V.
Hợp chất quan trọng có số OXH là +III và +V, riêng N có số OXH –III.
Qui luật biến đổi
Từ N  P độ bền số OXH +III và +V tăng dần vì có AO nd tham gia liên kết.
Từ P  Bi độ bền số OXH +III tăng còn +V giảm dần do tính trơ của cặp ns tăng dần từ trên xuống.
Tính KH của X(III) giảm dần, tính OXH của X(V) tăng dần từ P  Bi.
Department of Inorganic Chemistry - HUT
ĐẶC ĐIỂM CHUNG
Department of Inorganic Chemistry - HUT
ĐẶC ĐIỂM CHUNG
NITO
Đơn chất
Amoniac
Oxit của nito
Nitrit
Axit nitric
PHOTPHO
Đơn chất
Oxit và oxiaxit của photpho
ASEN, ANTIMON, BITMUS
Department of Inorganic Chemistry - HUT
1.095 Å
941 kJ/mol
Mp = - 210 oC
Bp = - 196 oC (77 K)
Department of Inorganic Chemistry - HUT
N
N2
N
Department of Inorganic Chemistry - HUT
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 fertilizer, and later still, as a chemical feedstock.
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 6 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 chemical substance can be determined by the Kjeldahl method.
Nitrogen compounds of notable economic 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 nitroprusside which regulate blood pressure and heart action by mimicing the action of nitric oxide.
Department of Inorganic Chemistry - HUT








Department of Inorganic Chemistry - HUT
Distillation
Department of Inorganic Chemistry - HUT
N
NH3
H
Mp = - 78 oC
Bp = - 33 oC
Tồn tại liên kết hidro
Tan 700 lit khí NH3 trong 1 lít nước
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Bazo
Khử
Thế hidro
Department of Inorganic Chemistry - HUT
Amoni cacbamat
Ure
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
amidua
Nitrua
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 camel dung 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 + 2 CaO → CaCl2 + Ca(OH)2 + 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 + 3 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 + 3 H2 → CH4 + H2O
CO2 + 4 H2 → CH4 + 2 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 → 2 NH3
The steam reforming, shift conversion, carbon dioxide removal and methanation steps each operate at absolute pressures of about 25 to 35 bar, and the ammonia synthesis loop operates at absolute pressures ranging from 60 to 180 bar depending upon which proprietary design is used. There are many engineering and construction companies that offer proprietary designs for ammonia synthesis plants. Haldor Topsoe of Denmark, Lurgi AG of Germany, and Kellogg, Brown and Root of the United States are among the most experienced companies in that field.[9]
Department of Inorganic Chemistry - HUT
Hiệu suất chuyển hóa ~ 17 %
Haber Process
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 + 5 O2 → 4 NO + 6 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 do 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.
During the 1960s, Tobacco companies such as Brown & Williamson and Philip Morris began using ammonia in cigarettes. The addition of ammonia serves to enhance the delivery of nicotine into the blood stream. As a result the reinforcement effect of the nicotine was enhanced, increasing its addictive ability without actually increasing the portion of nicotine.[12]
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Tính chất khử
Tính chất oxi hóa
Department of Inorganic Chemistry - HUT
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 sample with sulfanilic acid and naphthyl-1-amine in the presence of acid.[2]
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
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.
One use for nitric acid is in a colorometric test to tell the difference between heroin and morphine
Department of Inorganic Chemistry - HUT
ĐẶC ĐIỂM CHUNG
NITO
Đơn chất
Amoniac
Oxit của nito
Nitrit
Axit nitric
PHOTPHO
Đơn chất
Oxit và oxiaxit của photpho
ASEN, ANTIMON, BITMUS
P∞
Mp ~ 600 oC
P4
Mp ~ 44.2 oC
Ít bền
Oxi hóa chậm phát lân quang
Bốc cháy ở 35 oC  bảo quản trong khí trơ hoặc nước
Department of Inorganic Chemistry - HUT
Tính oxi hóa
Tính khử
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.
32P and 33P are used as radioactive tracers in biochemical laboratories (see Isotopes).
Department of Inorganic Chemistry - HUT
P
P4O10  H3PO4
P4S3, P4S10
PCl3, PCl5, POCl3
Thuốc trừ sâu
Department of Inorganic Chemistry - HUT
Axit metaphotphoric
Axit diphotphoric
Axit orthophotphoric
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
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.
Department of Inorganic Chemistry - HUT
ĐẶC ĐIỂM CHUNG
NITO
Đơn chất
Amoniac
Oxit của nito
Nitrit
Axit nitric
PHOTPHO
Đơn chất
Oxit và oxiaxit của photpho
ASEN, ANTIMON, BITMUS
Department of Inorganic Chemistry - HUT
Sb trong không khí ở nhiệt độ thường không biến đổi.
As, Bi bị oxi hóa trên bề mặt.
Khi đun nóng, đều tạo oxit với số OXH +III.
Ở dạng bột mịn đều cháy trong khí quyển Clo ở nhiệt độ thường tạo triclorua XCl3.
Khi đun nóng phản ứng với cả Br, I, S và một số kim loại.
 Thể hiện tính khử.
Department of Inorganic Chemistry - HUT
Không tác dụng với nước.
Không đẩy hidro ra khỏi axit.
Tính bền số OXH +V giảm dần  tính OXH tăng dần
Tính bền số OXH +III tăng dần  tính KH giảm dần
Department of Inorganic Chemistry - HUT
Bi3+ có tính khử yếu  chỉ tạo Bi5+ với chất OXH mạnh trong môi trường kiềm mạnh và đặc.
Bi5+ có tính oxi hóa mạnh
Tính OXH trung bình trong môi trường axit
Tính KH trung bình trong môi trường kiềm, trung tính
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Axit asenic
Axit asenơ
Axit metaasenơ
Department of Inorganic Chemistry - HUT
Department of Inorganic Chemistry - HUT
Antimonyl clorua
Bitmutyl nitrate
Department of Inorganic Chemistry - HUT
BÀI TẬP
Thứ 5: 1-3-2007
Bài: 1 đến 6
Chương 2: Hidro & Halogen