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

eletronegati
vidade

ponto de
fuso (0C)

abundncia
na terra
(ppm)

2,5

3930

320

(kJ mol-1)
C

0,77

1086

3550 (g)

Si

1,17

786

1,8

1420

277.200

Ge

1,22

760

1,8

949

Sn

1,40

707

1,8

232

40

Pb

1,46

715

1,8

327

16

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

, O2

PbS + 2PbO 3Pb + SO2

PbO + CO

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)

condies: 1800 0C, 70.000 atm.

carter metlico
ligao
C-C
Si-Si
Ge-Ge
Pb-Pb

energia de ligao (kJ mol-1)

348
222
167
155

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:
OH-

Si2H6 + H2O SiO2. nH2O + H2

germananos, estananos, plumbanos

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:

ex.: Sn(OH)4

HCl

SnCl4

H2O

HCl
H2O

[SnCl6]-2

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

silicones

O ciclo biogeoqumico do carbono

O aquecimento global do planeta

CO2
ENERGIA
SOLAR

RESPIRAO
DAS PLANTAS

DIXIDO DE CARBONO
(CO2) NO AR
CO2

FOGO

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

ALIMENTAO

RESPIRAO POR
PLANTAS
AQUTICAS,
ANIMAIS E
PROCESSOS DE
DECOMPOSIO

MILHES
DE ANOS

CARBONO FIXADO
EM CARBONATO DE
CLCIO DE MOLUSCOS

ALIMENTAO

MOLUSCOS

MILHES
DE ANOS

SEDIMENTAO
DE BIOMASSA

CO2

ERUPO
VULCNICA

QUEIMADAS

FIXAO DO
CARBONO PELA
FOTOSSINTESE EM
BIOMASSA DE
PLANTAS

CO2

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