GRUPO 15

GRUPO 15 Elementos: N, P, As, Sb, Bi Posio na tabela peridica configurao eletrnica: [...] n s2 n p3 n=2a6 estados de oxidao: As- 3; Sb- 3; Bi- 3, 5; P- 3, 5; N- 1, 2, 3; +4, +5

raio covalente (A) N P As Sb Bi 0,74 1,10 1,21 1,41 1,52

energia de eletronegati abundncia ionizao* vidade na terra (ppm) -1 (kJ mol ) 8838 5819 5629 4864 4780 3,0 2,1 2,0 1,9 1,9 46,3 1180 5 1 0,2

*- soma das 3 energias

Ocorrncia e obteno
N- atmosfera terrestre (78%), nitratos (NaNO3). Obtido por destilao fracionada do ar.
em laboratrio: NH4Cl + NaNO2 NH4NO2 N2 + 2 H2O 4NH3 + 3Ca(OCl)2 3CaCl2 + 6H2O + 2N2 2NaN3 2Na + 3N2

N:

used in ammonia, NH3, production (Haber process). This is the

greatest use of nitrogen. Ammonia is used for fertilizer production and to produce nitric acid (Ostwald process)

used used

by the electronics industry, which uses the gas as a blanketing medium during production of such components as transistors, diodes, etc. as a refrigerant (PE= -195,8 0C) both for the immersion freezing of food products and for transportation of foods wells to force crude oil upward

liquid nitrogen is used by the oil industry to build up pressure in used as an inert atmosphere in explosive liquid storage tanks,
both in ground-based tanks and in ships

 Nitrogen is a key component of biological molecules such as proteins (which are made from amino acids), and nucleic acids. ~26g/kg no corpo humano.

fertilizantes: (NH4)2SO4, uria- (NH2)2CO

amnia: processo Haber

! !

esta reao exotrmica! Por que usar ento 450 0C?

Nature 427, 527 - 530 (05 February 2004); doi:10.1038/nature02274

Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex

JAIME A. POOL, EMIL LOBKOVSKY & PAUL J. CHIRIK

P- rochas fosfatadas. Obtido por reduo com carbono e

silcio, em forno eltrico a 1300 0C

2Ca3(PO4)2 + 6SiO2 6CaSiO3 + P4O10 P4O10 + 10C P + 10CO

2Ca3(PO4)2(s) + 10C(s) + 6SiO2(s) P4(s) + 10CO +6CaSio3(s)

 used in the manufacture of safety matches, pyrotechnics, incendiary shells, smoke bombs fertilisers Na3PO4 is important as a cleaning agent, as a water softener, and for preventing boiler scale and corrosion of pipes and boiler tubes pesticides Phosphorus is a key component of biological molecules such as DNA and RNA. Phosphorus is a component of bones, and teeth, and many other compounds required for life. Chronic poisoning of people working unprotected with white phosphorus leads to necrosis of the jaw ~11g/kg no corpo humano.

superfosfato e superfosfato triplo:

Ca2H2(PO4)2 + CaSO4 Ca3H3(PO4)3

produo de cido fosfrico (maior consumo)

As:
realgar (As4S4), orpiment (As2S3), arsenolita (As2O3), arsenopirita (FeAsS) e loelingita (FeAs2) FeAsS (700C) FeS + As(g) As(s) doping agent in solid-state devices such as transistors the arsenide is used as a laser material to convert electricity directly into coherent light despite its poisonous reputation, may be a necessary ultratrace element for humans. It is a necessary ultratrace element for red algae, chickens, rats, goats, and pigs. A deficiency results in inhibited growth.

combate malria: arsenatos orgnicos

C&EN

Bi:

bismita (Bi2O3), bismutinita (Bi2S3), e bismutita [(BiO)2CO3 ]. Subproduto das plantas de produo de cobre, chumbo, estanho, prata, ouro e zinco. A etapa final envolve reduo do xido por carvo mineral. used in producing malleable irons as a catalyst for making acrylic fibres as a thermocouple material cosmetics Bismuth has no biological role. However it has been used for some time as a medicine (tripotassium dicitratobismuthate) for treatment of stomach upsets. In combination with antibiotics it is now used for treatment of some stomach ulcers.

Sb:
Stibinita (Sb2S3) e ulmanita (NiSbS). Sb2S3 + 3Fe 2Sb + 3FeS 2Sb2O3 +3C 4Sb + 3CO2 used in semiconductor technology for making infrared detectors, diodes, and Hall-effect devices used in alloys with percentages ranging from 1 to 20 - greatly increases the hardness and mechanical strength of lead batteries oxides, sulphides, sodium antimonate, and antimony trichloride are used in manufacturing flame-proofing compounds tartar emetic (hydrated potassium antimonyltartate) is used in medicine

 Antimony has no biological role. In small doses it is said to stimulate the metabolism. Combate Leishmaniose: antimoniatos

propriedades
carter metlico- varia de no-metais (N, P) a metais (Bi) estruturas: N2- gs fsforo branco (tetraedro C4), fsforo vermelho (polimerizada), fsforo preto As e Sb- forma tetradrica e metlica Bi- forma metlica o on M+5 no existe (Eioniz muito alta!) Sb e Bi podem existir como M+3, porm s formam compostos inicos com o fluor (SbF3, BiF3)

o nitrognio capaz de formar ligaes mltiplas p-p fortes (*). Seu nmero de coordenao mximo quatro. os outros elementos podem ter nmero de coordenao cinco ou seis.

compostos
xidos
xidos de nitrognio vo dos neutros aos cidos N2O; NO; NO2 N2O4; N2O3; N2O5; NO3; N2O6 NO- diamagntico no estado slido, com formao de dmeros. No estado gasoso paramagntico. Reage com halognios, formando haletos de nitrosila (ex. NOCl), atuando ainda como ligante na presena de metais de transio.

N2

October 12, 1998 The Nobel Assembly at Karolinska Institutet has today decided to award the Nobel Prize in Physiology or Medicine for 1998 jointly to

Robert F. Furchgott, Louis J. Ignarro and Ferid Murad

for their discoveries concerning "nitric oxide as a signalling molecule in the cardiovascular system". Summary Nitric oxide (NO) is a gas that transmits signals in the organism. Signal transmission by a gas that is produced by one cell, penetrates through membranes and regulates the function of another cell represents an entirely new principle for signalling in biological systems. The discoverers of NO as a signal molecule are awarded this year's Nobel Prize.

http://www.nobel.se/medicine/laureates/1998/

Nitric oxide protects the heart, stimulates the brain, kills bacteria, etc. It was a sensation that this simple, common air pollutant, which is formed when nitrogen burns, for instance in automobile exhaust fumes, could exert important functions in the organism. It was particularly surprising since NO is totally different from any other known signal molecule and so unstable that it is converted to nitrate and nitrite within 10 seconds. NO was known to be produced in bacteria but this simple molecule was not expected to be important in higher animals such as mammals. NO is a signal molecule of key importance for the cardiovascular system and it was also found to exert a series of other functions. We know today that NO acts as a signal molecule in the nervous system, as a weapon against infections, as a regulator of blood pressure and as a gatekeeper of blood flow to different organs. NO is present in most living creatures and made by many different types of cells. - When NO is produced by the innermost cell layer of the arteries, the endothelium, it rapidly spreads through the cell membranes to the underlying muscle cells. Their contraction is turned off by NO, resulting in a dilatation of the arteries. In this way, NO controls the blood pressure and its distribution. It also prevents the formation of thrombi. - When NO is formed in nerve cells, it spreads rapidly in all directions, activating all cells in the vicinity. This can modulate many functions, from behaviour to gastrointestinal motility. - When NO is produced in white blood cells (such as macrophages), huge quantities are achieved and become toxic to invading bacteria and parasites.

Diagnostic analyses: Inflammatory diseases can be revealed by analysing the production of NO from e.g. lungs and intestines. This is used for diagnosing asthma, colitis, and other diseases. NO is important for the olfactory sense and our capacity to recognise different scents. It may even be important for our memory. Nitroglycerin Alfred Nobel invented dynamite, a product in which the explosion-prone nitroglycerin is curbed by being absorbed in kieselguhr, a porous soil rich in shells of diatoms. When Nobel was taken ill with heart disease, his doctor prescribed nitroglycerin. Nobel refused to take it, knowing that it caused headache and ruling out that it could eliminate chest pain. In a letter, Nobel wrote: It is ironical that I am now ordered by my physician to eat nitroglycerin. It has been known since last century that the explosive, nitroglycerin, has beneficial effects against chest pain. However, it would take 100 years until it was clarified that nitroglycerin acts by releasing NO gas.

NO2- gs castanho-avermelhado em laboratrio: 2Pb(NO3)2 2PbO + 4NO2 + O2 Cu + 4HNO3 Cu(NO3)2 + 2NO2 + 2H2O N2O5- anidrido do cido ntrico Processo Ostwald para produo de cido ntrico 200 atm N2 + 3H2 2NH3 (processo Haber)
Fe, 500 0C

reao muito exotrmica*

5-10 atm

2NH3 + O2

Pt/Rh ~900 0C

NO NO2* HNO3

* 3NO2 + H2O 2HNO3 + NO

http://www.carlton.srsd119.ca/chemical/mtom/contents/chapter3/fritzhaber_2.htm

xidos de fsforo- formados pela combusto direta em presena de ar ou oxignio oxicidos: cidos fosfricos: P(V); cidos oxidantes

H3PO4- cido ortofosfrico

Ca3(PO4)2 + 3H2SO4 2H3PO4 + 3CaSO4 P4O10 + 6H2O 4H3PO4

P + HNO3 H3PO4
H3PO4
aquec.

H4P2O7
c. pirofosfrico

aquec. forte

(HPO3)n
c. metafosfrico

P4O10

P4O6

cidos fosforosos: P(III)

H3PO3- cido ortofosforoso

H3PO3 H4P2O5
c. pirofosforoso

(HPO2)n
c. metafosforoso

xidos de As, Sb e Bi: As4O6, As4O10, Sb4O6, Sb4O10, Bi2O3

haletos
trialetos (MX3)- todos os trialetos so conhecidos, sendo o de nitrognio o menos estvel. Tm estruturas tetradricas, com um dos vrtices ocupados por um par de eltrons livres. So predominantemente covalentes. pentaletos (MX5)- o nico que no pode form-los o nitrognio (por que?) PF5, PCl5, PBr5, AsF5, SbF5

hidretos
todos os elementos formam hidretos volteis, com frmula geral AH3. a formao de ligaes com o par de eltrons livres diminui do N para o Bi.

a estabilidade dos hidretos decresce de cima para baixo, com a diminuio da energia de ligao A-H.

sp3

pKa=9,25

NITROGNIO ( N2 ) GASOSO NO AR FIXAO BIOLGICA POR LEGUMINOSAS E CIANOBACTRIAS DESNITRIFICAO FIXAO ATMOSFRICA FERTILIZANTES NITROGENADOS
BACTRIAS NO SOLO

FIXAO INDUSTRIAL

ADUBO

NITRATOS ( NO3- )

CULTIVARES NO LEGUMINOSAS

PLANTAS NO FIXADORAS DE NITROGNIO

ALIMENTAO E EXCREO ANIMAL

BACTRIAS NO SOLO

SAIS DE AMNIO ( NH4+ )

ALIMENTAO E EXCREO ANIMAL

Ciclo do nitrogenio

Eventos recentes
Los Angeles - primeiras observaes do Smog fotoqumico so feitas ainda nos anos 40

Sun

Solar radiation in urban area

+ Organic compounds NOx (nitrogen oxides) (hydrocarbons)

With the presence of an inversion layer, trapping pollutants

Concentrated photochemical smog (brown air)

R1 C H R1 . O H C C C

R2

R1

R2

+ OH.
H R2 OH H R2 .C O+ H OH H NO

. C

C H R1

OH O2 R2

. O

O H

C H

OH

+
NO2. R1 C H

R2

O2
H

O + .OOH

NO2 .

hv v

NO . + O
O3 HNO3

O + O2 HO. + NO2 .

HO. + NO .
hv

HONO

NO2 . + O3

NO3 + O2
NO2 , H2O

HNO3, R