Cristaloquímica - Ligações Químicas

Cristalografia e Gemologia

•
UFVJM

Kethelle D'Ars
12/07/2019
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CRISTALOQUÍMICA	
  
UFVJM/ICT	
  
ENGENHARIA	
  GEOLÓGICA	
  
JOSÉ	
  MARIA	
  LEAL	
  
Abundância	
  dos	
  elementos	
  químicos	
  na	
  Crosta	
  
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Os	
  oitos	
  elementos	
  mais	
  abundantes	
  na	
  crosta	
  terrestre	
  (Klein	
  
&	
  Hurbult,	
  1999)	
  
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Estes	
  são	
  os	
  elementos	
  cons;tuintes	
  da	
  maioria	
  dos	
  minerais	
  
Ligações	
  Químicas	
  (LQ)	
  	
  
O	
  Tipo	
  e	
  intensidade	
  das	
  ligações	
  químicas	
  são	
  responsáveis	
  
pelas	
  propriedades	
  Hsicas	
  e	
  químicas	
  dos	
  minerais	
  
Em	
  geral,	
  quanto	
  MAIS	
  FORTE	
  for	
  a	
  ligação	
  química	
  MAIS	
  DURO	
  é	
  o	
  
cristal	
  
MAIS	
  ELEVADO	
  é	
  o	
  Ponto	
  de	
  FUSÃO	
  e	
  MENOR	
  é	
  o	
  COEFICIENTE	
  DE	
  
EXPANSÃO	
  TERMAL	
  
LQ	
  agrupam	
  2	
  categorias	
  
Ligações	
  que	
  envolvem	
  Elétrons	
  de	
  Valência	
  	
  
Iónicas	
  
Covalentes	
  
Metálicas	
  
Ligações	
  que	
  não	
  envolvem	
  os	
  Elétrons	
  de	
  Valência	
  
Van	
  der	
  Waals	
  
Hidrogênio	
  
Todos	
  os	
  92	
  elementos	
  que	
  ocorrem	
  na	
  natureza,	
  exceto	
  os	
  gases	
  
nobres	
  (He,	
  Ne,	
  Ar,	
  Kr,	
  Xe	
  e	
  Rn),	
  formam	
  ligações	
  químicas	
  uns	
  com	
  
os	
  outros,	
  sejam	
  entre	
  o	
  mesmo	
  elemento	
  ou	
  entre	
  elementos	
  
diferentes	
  
A	
  caracterís;ca	
  comum	
  aos	
  gases	
  nobres	
  que	
  explica	
  este	
  
comportamento	
  é	
  a	
  presença	
  de	
  orbitais	
  externos	
  
completamente	
  preenchidos	
  por	
  elétrons,	
  faltando,	
  
portanto,	
  elétrons	
  de	
  valência	
  
A	
  falta	
  de	
  rea;vidade	
  química	
  sugere	
  que	
  a	
  conﬁguração	
  
eletrônica	
  apresentada	
  pelos	
  gases	
  nobres	
  é	
  uma	
  
conﬁguração	
  de	
  baixa	
  energia	
  ou	
  estável	
  
Os	
  outros	
  elementos	
  tendem	
  a	
  adquirir	
  uma	
  
conﬁguração	
  eletrônica	
  mais	
  estável,	
  idên;ca	
  à	
  dos	
  
gases	
  nobres,	
  ganhando,	
  perdendo	
  ou	
  par`lhando	
  
elétrons	
  de	
  valência	
  
Ligações	
  	
  Iônicas	
  
Ocorre	
  quando	
  um	
  ou	
  mais	
  elétrons	
  nas	
  camadas	
  de	
  
valência	
  de	
  um	
  átomo	
  são	
  transferidos	
  para	
  a	
  camada	
  
de	
  valência	
  de	
  outro	
  átomo,	
  de	
  forma	
  que	
  ambos	
  
alcançam	
  a	
  confuguração	
  de	
  um	
  gás	
  inerte.	
  
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Uma	
  ligação	
  iônica	
  pode	
  ser	
  
deﬁnida	
  como	
  a	
  atração	
  entre	
  
íons	
  de	
  cargas	
  opostas	
  
Ligações	
  Iônicas	
  são	
  os	
  resultado	
  da	
  TROCA	
  de	
  ELÉTRONS	
  
entre	
  um	
  átomo	
  de	
  um	
  metal	
  (formando	
  um	
  cá;on)	
  e	
  um	
  
átomo	
  de	
  um	
  não	
  metal	
  (formando	
  um	
  ánion.	
  
Os	
  cristais	
  com	
  ligações	
  iônicas	
  têm	
  dureza	
  e	
  peso	
  
especíﬁco	
  moderados,	
  pontos	
  de	
  fusão	
  razoalvelmente	
  
elevados	
  e	
  são	
  maus	
  condutores	
  de	
  eletricidade	
  e	
  de	
  
calor.	
  São	
  maus	
  condutores	
  elétricos	
  devido	
  à	
  estabilidade	
  
dos	
  íons	
  que	
  não	
  ganham	
  nem	
  perdem	
  elétrons	
  com	
  
facilidade.	
  
Ligações	
  Covalentes	
  
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Os	
  íons	
  de	
  cloro	
  podem	
  cons;tuir	
  unidades	
  estáveis	
  em	
  cristais	
  
com	
  ligações	
  iônicas	
  porque	
  o	
  seu	
  orbital	
  externo	
  ﬁca	
  preenchido	
  
adquirindo	
  um	
  elétron	
  de	
  um	
  metal,	
  como	
  o	
  Na.	
  Um	
  átomo	
  isolado	
  
de	
  cloro	
  com	
  um	
  orbital	
  de	
  valência	
  incompleta	
  pode	
  com	
  binar-‐se	
  
com	
  um	
  outro	
  átomo	
  de	
  cloro,	
  de	
  forma	
  que	
  os	
  dois	
  elétrons	
  de	
  
valência,	
  um	
  de	
  cada	
  átomo.	
  Completam	
  os	
  orbitais	
  de	
  ambos	
  os	
  
átomos	
  e	
  adiquirem	
  a	
  conﬁguração	
  de	
  um	
  gás	
  inerte	
  	
  
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As	
  ligações	
  covalentes	
  são	
  ligações	
  químicas	
  que	
  
resultam	
  da	
  par;lha	
  de	
  elétrons	
  entre	
  átomos	
  
Ligações	
  Covalentes	
  ocorrem	
  quando	
  os	
  orbitais	
  de	
  dois	
  átomos	
  
se	
  sobrepõem.	
  O	
  par	
  de	
  elétrons	
  dos	
  orbitais	
  sobrepostos	
  move-‐
se	
  em	
  torno	
  de	
  dois	
  átomos.	
  A	
  intensidade	
  das	
  liagações	
  
covalentes	
  é	
  função	
  do	
  grau	
  de	
  sobreposição	
  dos	
  orbitais	
  de	
  
átomos	
  adjacentes.	
  No	
  diamante	
  o	
  alto	
  grau	
  de	
  sobreposição	
  
produz	
  ligações	
  muito	
  fortes,	
  que	
  se	
  reﬂetem	
  na	
  dureza.	
  
As	
  ligações	
  covalentes	
  cons;tuem	
  o	
  `po	
  de	
  ligação	
  química	
  
mais	
  forte.	
  Os	
  minerais	
  com	
  ligações	
  covalentes	
  são	
  
caracterizados	
  por	
  pontos	
  de	
  fusão	
  elevados,	
  grande	
  
estabilidade,	
  insolubilidade	
  e	
  não	
  são	
  condutores	
  de	
  
eletricidade,	
  tanto	
  no	
  estado	
  sólido	
  como	
  em	
  solução.	
  Poque	
  
as	
  forças	
  elétricas	
  que	
  cons;tuem	
  a	
  ligação	
  estão	
  localizadas	
  
na	
  vizinhança	
  dos	
  elétrons	
  par;lhados,	
  a	
  ligação	
  é	
  altamente	
  
direcional	
  e	
  a	
  simetria	
  dos	
  cristais	
  com	
  ligações	
  é	
  inferior	
  à	
  
dos	
  cristais	
  com	
  ligações	
  iônicas.	
  	
  
Ligações	
  Metálicas	
  
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As	
   L igações	
   Metá l i cas	
   podem	
   ser	
  
consideradas	
   como	
   um	
   ;po	
   de	
   ligação	
  
covalente	
  nas	
  quais	
  os	
  elétrons	
  de	
  valência	
  
são	
  livres	
  para	
  se	
  moverem	
  de	
  átomo	
  para	
  
átomo,	
   através	
   de	
   toda	
   estrutura	
  
cristalina.	
  
As	
   unidades	
   estruturais	
   dos	
   metais	
   são	
  
n ú c l e o s	
   e s f é r i c o s , 	
   c a r r e g a d o s	
  
posi;vamente,	
   ligados	
   por	
   uma	
   nuvem	
   de	
  
elétrons	
   de	
   valência	
   que	
   circundam	
   os	
  
núcleos.	
   Muitos	
   dos	
   elétrons	
   não	
   têm	
  
aﬁnidade	
  com	
  qualquer	
  núcleo	
  par;cular	
  e	
  
são	
   livres	
   para	
   se	
  moverem	
   na	
   estrutura,	
  
ou	
  mesmo	
  for	
  a	
  dela	
  
Este	
   ;po	
   de	
   ligação	
   é	
   responsável	
   pela	
   elevada	
   plas;cidade,	
  
duc;lidade,	
  condu;bilidade	
  e	
  baixa	
  dureza	
  dos	
  metais.	
  Só	
  os	
  metais	
  
na;vos	
  apresentam	
  ligações	
  metálicas	
  puras.	
  
Ligações	
  de	
  Van	
  der	
  Waals	
  
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748,-9&)!5/=,7&*+&)!;EBFFB?!O###>I!A/7,(4<,-./!6,)!7M24*,)!6&!5,(N/*/!6&=46/!P!5/*5&*+(,-./!
6&!&7&5+(9&)!*12!6/)! 7,6/)!6/)!3+/2/)?!/(484*,*6/!12!&L&4+/!64'/7,(I!Q)! 748,-9&)!6&!=,*!6&(!
K,,7)! )./! '(/61<46,)! '/(! ,+(,5-./! &7&5+(/)+3+45,! L(,5,! &*+(&! 5,(8,)! /'/)+,)! *,! )1'&(LR54&! 6&!
7M24*,)!,6S,5&*+&)I!,.-'B)01&2,?!&2!'&()'&5+4=,?!6,!&)+(1+1(,!6,!8(,L4+&!;CJBDE!T!UV%JWVX?!
"GGG>I!E/+,(!/!&)',-,2&*+/!(&7,+4=,2&*+&!7,(8/!;Y?Y$Z>!&*+(&!,)!5,2,6,)I!
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As	
  ligações	
  de	
  
Van	
  der	
  Waals	
  
são	
  ligações	
  
químicas	
  mais	
  
fracas,	
  mas	
  
mantém	
  ligadas	
  
moléculas	
  
neutras,	
  numa	
  
estrutura	
  coesa,	
  
devido	
  a	
  
pequenas	
  cargas	
  
residuais	
  nas	
  
superacies.	
  	
  
Normalmente,	
  deﬁnem	
  	
  uma	
  zona	
  de	
  clivagem	
  
fácil	
  e	
  baixa	
  dureza.	
  
	
  
Ex:	
  graﬁta,	
  talco	
  e	
  o	
  enxofre	
  cristalino	
  
	
  
	
  No	
  enxofre,	
  este	
  ;po	
  de	
  ligação	
  química	
  é	
  
responsável	
  pela	
  baixa	
  dureza	
  (1,5	
  a	
  2,5)	
  e	
  baixo	
  
ponto	
  de	
  fusão	
  (112,8o).	
  	
  
Ligação	
  de	
  Van	
  der	
  WaalsLigações	
  de	
  Hidrogênio	
  
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=0C(<+2D+,!+2D/+!?!+!@B!?!=02,D&D>&!>E!2F=<+0!=(//+'(-0!A0,&D&C(E+2D+B!(!-&,D/&G>&)H0!-(!=(/'(!1!
D+D/(1-/&=(:!+-,!I(-(!2J!2+'(D&C0!2(!E0<1=><(!(D/(&!>E!2J!A0,&D&C0!3KD0E0!-+!?9!2(!E0<1=><(!-+!
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$!(2&*+,!W!+E!D0/20!-0!=(D&H0!I:!+-,!I02-&)H0!<&E&D+!A(/(!(!=00/-+2()H0!=FG&=(!3S=XS(Y#7Z[89:!
+/,! I00/-+2()H0! 0=D(1-/&=(! -+! \! (2&*+,!W! +E! D0/20! -0! =(D&H0!I:' +0,'I02-&)H0! <&E&D+! A(/(! (!
=00/-+2()H0!0=D(1-/&=(!3S=XS(]#7Z[8^#:_"_9:!
Moléculas	
  polares	
  podem	
  formar	
  estruturas	
  cristalinas	
  
devido	
  à	
  atração	
  entre	
  terminações	
  das	
  moléculas	
  com	
  
carga	
  oposta	
  
! "#$! !! "#$
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!"#$%&' ()*! %&'()*+,! -+! .&-/0'12&0! 3456657! 8###9:! +&,! ;0<1=><(! ?8@! A0<(/B! <&'()*+,!
=0C(<+2D+,!+2D/+!?!+!@B!?!=02,D&D>&!>E!2F=<+0!=(//+'(-0!A0,&D&C(E+2D+B!(!-&,D/&G>&)H0!-(!=(/'(!1!
D+D/(1-/&=(:!+-,!I(-(!2J!2+'(D&C0!2(!E0<1=><(!(D/(&!>E!2J!A0,&D&C0!3KD0E0!-+!?9!2(!E0<1=><(!-+!
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$!(2&*+,!W!+E!D0/20!-0!=(D&H0!I:!+-,!I02-&)H0!<&E&D+!A(/(!(!=00/-+2()H0!=FG&=(!3S=XS(Y#7Z[89:!
+/,! I00/-+2()H0! 0=D(1-/&=(! -+! \! (2&*+,!W! +E! D0/20! -0! =(D&H0!I:' +0,'I02-&)H0! <&E&D+! A(/(! (!
=00/-+2()H0!0=D(1-/&=(!3S=XS(]#7Z[8^#:_"_9:!
Nas	
  moléculas	
  de	
  H2O	
  as	
  ligações	
  entre	
  os	
  dois	
  átomos	
  de	
  
H	
  e	
  o	
  átomo	
  de	
  O	
  são	
  covalentes	
  	
  
Porque	
  o	
  oxigênio	
  é	
  mais	
  eletronega;vo	
  a	
  molécula	
  resultante	
  é	
  
polar	
  –	
  posi;va	
  próxima	
  dos	
  dois	
  núcleos	
  de	
  hidrogênio	
  e	
  nega;va	
  
nos	
  dois	
  nós	
  oposto	
  ao	
  oxigênio.	
  
As	
  cargas	
  nega;vas	
  e	
  posi;vas	
  concentram-‐se	
  nos	
  vér;ces	
  de	
  um	
  
tetraedro	
  
Se	
  as	
  temperaturas	
  
forem	
  suﬁcientes	
  
baixas	
  (<0o	
  C),	
  atrações	
  
eletrostá`cas	
  fracas	
  
entre	
  as	
  moléculas	
  
polares	
  podem	
  mantê-‐
las	
  unidas	
  (gelo)	
  
As	
  ligações	
  de	
  hidrogênio	
  são	
  comuns	
  em	
  alguns	
  
hidróxidos,	
  nos	
  quais	
  o	
  grupo	
  (OH)-‐	
  não	
  se	
  
comporta	
  estritamente	
  como	
  um	
  grupo	
  aniônico	
  
esférico,	
  mas	
  é	
  mais	
  realis`camente	
  representado	
  
por	
  uma	
  coordenação	
  assimétrica,	
  que	
  produz	
  um	
  
efeito	
  dipolar.	
  Estão	
  também	
  presentes	
  em	
  muitos	
  
silicatos	
  lamelares,	
  como	
  as	
  micas	
  e	
  minerais	
  de	
  
argila,	
  que	
  contém	
  o	
  grupo	
  hidróxilo	
  
Ligações	
  de	
  Hidrogênio	
  	
  
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Resumo das propriedades conferidas pelos principais tipos de ligações químicas 
Regras	
  de	
  Pauling	
  
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