GRUPO 14

GRUPO 14 Elementos: C, Si, Ge, Sn, Pb Posio na tabela peridica configurao eletrnica: [...] n s2 n p2 n=2a6 estados de oxidao: C- IV (II); Si- IV; Ge- IV; Sn- II, IV; Pb- II, IV

metais, no-metais e semi-condutores

raio covalente (A)

1a energia de ionizao (kJ mol-1)

eletronegati vidade

ponto de fuso (0C)

abundncia na terra (ppm)

C Si Ge Sn Pb

0,77 1,17 1,22 1,40 1,46

1086 786 760 707 715

2,5 1,8 1,8 1,8 1,8

3930
3550 (g)

320 277.200 7 40 16

1420 949 232 327

quarta energia de ionizao muito alta (3.800 a 6.200 kJ mol-1) compostos inicos com o on M+4 so raros (SnF4, PbF4, SnO2, PbO2)

 Ocorrncia e obteno: i) C- jazidas de carvo, petrleo, calcita (CaCO3), magnesita (MgCO3), carvo vegetal ii) Si- slica (SiO2) e silicatos com diversas estruturas iii) Ge- traos em minrios de prata e zinco iv) Sn- cassiterita (SnO2) v) Pb- galena (PbS)

(Si, Ge, Sn)O2 + C CO2 + Si (Ge, Sn)

, O2

3PbS PbS

PbS + 2PbO 3Pb + SO2 PbO + CO

, O2

Pb + CO2

alotropia
C- diamante, grafite e fulerenos Sn- Sn (cinza, diamante) Sn (branco, metlico) Si, Ge- estrutura similar ao diamante

Si

lubrificantes eletrodos lpis e minas (grafite + talco)

C60

K3C60 (supercondutor a T<18 K)

paredes concntricas formadas por anis C6 interconectados

aplicaes
C: fuel (coal) lubricant (graphite) C-14 isotope used in archaeological dating carbon compounds are important in many facets of the chemical industry Carbon is key to life and by definition is present in all organic compounds Ethene gas (C2H4) helps to ripen tomatoes ~230 g/kg de massa no corpo humano no Universo ~5.000 ppm (5 g/kg)

Si: doped with boron, gallium, phosphorus, or arsenic, etc. to produce silicon for use in transistors, solar cells, rectifiers, and other electronic solid-state devices silica, as sand, is a principal ingredient of glass, a material with excellent mechanical, optical, thermal, and electrical properties computer chips lubricants used in medicine for silicone implants

Diamond chips coming (Nature, sep/02)

O espao de entorno dos gros bloqueia o fluxo de corrente

Deposio qumica de vapor

nanotubos

Graphene (no um altropo do carbono) Graphene has a similar structure to graphite but is a single isolated sheet of carbon. (espessura de um tomo; futuros chips de computadores?) Andre Geim e Konstantin Novoselov; premio Nobel de Fsica em 2010
http://www.ewels.info/img/science/nanotubes/nanomovie.new.mpg

 Diatoms, some protozoa, some sponges, and some plants use silicon dioxide (SiO2) as a structural material. Silicon is known to be required by chicks and rats for growth and skeletal development. Silicon is not particularly toxic but finely divided silicates or silica cause major damage to lungs. ~0,26 g/kg no corpo humano

Ge: doped with arsenic, gallium, or other elements for use as a transistor element. Its application as a semiconductor provides the largest use for germanium germanium and germanium oxide are transparent to the infrared and are used in infrared spectroscopes and other optical equipment, including extremely sensitive infrared detectors. Also for wide-angle camera lenses and microscope objectives. possible chemotherapy applications?

Sn: used to coat other metals to prevent corrosion or other chemical action (tin cans are made from tin coated steel) alloying agent- important alloys include soft solder, type metal, fusible metal, bronze, bell metal, White metal and phosphor bronze the chloride (SnCl2.H2O) is used as a reducing agent a crystalline tin-niobium alloy is superconductive at very low temperatures. Such magnets, made of tin-niobium wire, weigh just a few pounds and produce magnetic fields that are comparable to that of a 100 ton electromagnet trialkyl and triaryl tin compounds are biocides there is concern over their environmental effects. Tributyltin is the active ingredient in a type of antifouling paint used on ships. ~0,2 mg/kg no corpo humano

Pb: storage batteries manufacture of PbEt4 - an antiknock compound in petrol. Environmental concern with lead poisoning is resulting in less use of lead in petrol the metal is very effective as a sound absorber a radiation shield around X-ray equipment and nuclear reactors used extensively in paints, although recently the use of lead in paints has been drastically curtailed to eliminate or reduce health hazards the oxide is used in producing fine "crystal glass" and "flint glass" with a high refractive index for achromatic lenses solder

 used by the Romans for plumbing (the decline of the Roman empire is attributed to lead in the water supply!) used to contain corrosive liquids alloying cable covering ammunition insecticides Lead has no biological role. Lead affects the gut, central nervous system and causes anaemia.

lead coordinates three sulfurs in structural binding sites of proteins even when four sulfurs are available, unlike zinc, which uses tetrahedral coordination. When the zinc in proteins is substituted with lead, the resulting proteins cannot function The chemical literature has widely suggested that lead binds sulfur in a fourcoordinate fashion
C&EN VOLUME 83, ISSUE 26
June 27, 2005

Propriedades e compostos C(g) C(d) carter metlico ligao C-C Si-Si Ge-Ge Pb-Pb energia de ligao (kJ mol-1) 348 222 167 155 condies: 1800 0C, 70.000 atm.

C- grande capacidade para a formao de cadeias e ligaes mltiplas

compostos covalentes e tetravalentes hibridizao reatividade: aumentando do C para o Pb

C- reao com o F2 Si- reao com HF Ge- reao com H2SO4 e HNO3 Sn, Pb- reao com diversos cidos

efeito do par inerte: com a descida no grupo, o numero de oxidao II vai se tornando o mais estvel

xidos
CO: xido neutro, pouco solvel em gua forma-se por oxidao incompleta do carbono

mtodos de obteno industrial:

HCOOH + H2SO4 CO + H2O C + H2O CO + H2 (gs dgua) importante combustvel
2CO + O2 2CO2 565 kJ mol-1

usado como agente redutor: Fe2O3 + 3CO 2Fe + 3CO2 (altos-fornos) CuO + CO Cu + CO2 compostos carbonil-metal:
ex.: Ni(CO)4, sendo o CO um ligante (interao pd)
(processo Mond para obteno de Ni metlico)

reage com O, S, F, Cl e Br

CO2:
xido cido com estrutura linear (sp) obtido por ataque de cidos diludos sobre carbonatos, por combusto completa do carbono ou por aquecimento do calcreo: CaCO3(s) + HCl(aq) CaCl2(aq) + CO2 + H2O C + O2 CO2 CaCO3 CaO(s) + CO2 slido, sublima a -78 0C

importncia
fotosntese, respirao, fermentao

*
O gs em refrigerantes

efeito estufa e aquecimento global

CO2

CO

CO32

SiO2 (slica):
slido tridimensional de elevado ponto de fuso, existindo em trs tipos distintos de estrutura: quartzo, tridimita e cristobalita. atacada por F2, HF e lcalis: SiO2 + HF SiF4 Si(OH)4 SiO2 + NaOH Na2SiO3 (Na4SiO4)
H2O

empregos: componentes pticos, vidros, catalisadores, agentes dessecantes.

SiO2

Silicone

SiO4

asbestos

piroxnio
mica

siOcage

Ge, Sn, Pb:

a basicidade aumenta de cima para baixo: SnO2, PbO2: anfteros
PB3O4 (2PbO . PbO2): xido vermelho de chumbo, usado como pigmento PbO: cermicas PbO2: baterias

hidretos
os hidretos formados so covalentes
C- alcanos, alcenos, ... Si- silanos (SinH2n+2)

(n 8 )

silanos so redutores, queimam ao ar e sofrem hidrlise em meio alcalino: Si2H6 + H2O SiO2. nH2O + H2
germananos, estananos, plumbanos
OH-

haletos
tetraaletos- so tetradricos e quase todos volteis e covalentes, com exceo de SnF4 e PbF4 poli(fluorcarbonetos): CF4(CF2)nCF4: Teflon (Du Pont) clorofluorcarbonetos: CF2Cl2, CFCl3, etc: Freons (Du Pont)
a depleo da camada de oznio

haletos de silcio: hidrolisveis SiCl4 + 4H2O Si(OH)4 + 4HCl

SiF4 + 4H2O Si(OH)4 + 4HF SiF4 [SiF6]-2 + 2H+

(geometria e hibridizao?)

Ge, Sn, Pb- seus tetraaletos (MX4) tambm so hidrolisveis, podendo entretanto ser reversvel a reao:
HCl H2O HCl H2O

ex.: Sn(OH)4

SnCl4

[SnCl6]-2

estabilidade dos dialetos: CX2 < SiX2 < GeX2 < SnX2 < PbX2

silicones

O ciclo biogeoqumico do carbono

O aquecimento global do planeta

CO2 ENERGIA SOLAR DIXIDO DE CARBONO (CO2) NO AR CO2 CO2 CO2

RESPIRAO DAS PLANTAS

FOGO
QUEIMADAS

FIXAO DO CARBONO PELA FOTOSSINTESE EM BIOMASSA DE PLANTAS

ERUPO VULCNICA RESPIRAO POR PLANTAS AQUTICAS, ANIMAIS E PROCESSOS DE DECOMPOSIO

ALIMENTAO

MILHES DE ANOS

DISSOLUO DO CO2 EM GUA, FIXAO DO CARBONO PELA FOTOSSINTESE EM BIOMASSA DE ALGAS E FITOPLANCTON

ALIMENTAO

CARBONO FIXADO EM CARBONATO DE CLCIO DE MOLUSCOS

MOLUSCOS

MILHES DE ANOS

SEDIMENTAO DE BIOMASSA

CONVERSO A CARVO, LEO, GS NATURAL (COMBUSTVEIS FSSEIS)

QUEIMA DE COMBUSTVEIS FSSIS

O efeito estufa

Absoro de radiao por CO2

Estocagem de carbono

NOTE: Current CO2 levels are 380-385 ppm. Nearly all potential geologic capacity is from deep saline formations. Figures were provided in metric tons of CO2 and converted to metric tons of carbon. SOURCE: J. J. Dooley, Battelle, Pacific Northwest National Laboratory Plenty of room: Potential world geologic storage for CO2 exceeds estimated need in the next century
C&EN April 2, 2007, Volume 85, Number 1, pp. 48-51