Teoria Estrutural

Universidade Federal do Cear
Centro de Cincias
Departamento de Qumica Orgnica e Inorgnica
Qumica Orgnica Terica I
TEORIA ESTRUTURAL
Professora: Dra. Antnia Torres vila Pimenta
Introduo s molculas orgnicas

A qumica orgnica comeou a florescer com a queda da
teoria da fora vital (sculo IX).

O qumico Berzelius acreditava que materiais como sangue, suor,
gordura, s poderiam ser sintetizados por organismos vivos.
SUBSTNCIAS ORGNICAS: Derivadas de

organismos vivos continham uma fora vital a
essncia da vida.
SUBSTNCIAS INORGNICAS: Derivadas de
fontes no vivas.
O nome qumica orgnica pr

ia possvel preparar um composto orgnico a partir de materiais
havia
publicada em 1828, um marco histrico na fragilizao
da duas categorias diferentes de substnc
1
provenientes dos seres vivos (animais ou ve
exclusivamente inorgnicos. A clssica sntese de Whler ,
Introduo
s
molculas
inorgnicos,orgnicas
provenientes dos minerais. Est
teoria de que os compostos orgnicos s poderiam ser
publicada em 1828, um marco histrico na fragilizao da
porque se pensava que os compostos orgnicos
sintetizados por organismos vivos: Whler obteve uria, um
qumicos podiam transformar um composto or
teoria de que os compostos orgnicos s poderiam ser
acreditava-se que no seria possvel preparar um
conhecido composto orgnico, por aquecimento de uma
exclusivamente ino
sintetizados
porentanto
organismos
vivos: Friedrich
Whler obteve
uria, um
No
em 1828,
Wohler
publicada em 1828
soluo aquosa de cianato de amnio, um composto
teoria de que os
conhecido composto
por aquecimento
de uma
sintetizou orgnico,
a uria (constituinte
da urina)
sintetizados por or
reconhecidamente inorgnico (pois ele podia ser preparado a
conhecido compo
soluo aquosa
dedocianato
amnio, um composto
a partir
cianatode
de amnio.
soluo aquosa d
partir de outros compostos inorgnicos).
reconhecidamente
reconhecidamente inorgnico (pois ele podia ser preparado a
partir de outros co
partir de outros compostos inorgnicos).
NH2
C
O
NH2
NH4CNO
NH4CNO
cianato de amnio
uria
NH2
NH4
Esquema 1.1.1. Sntese

de Whler
uria
cianato de amnio
cianato de
NH2
Esqu
primeira vista, a diviso

inorgnica deveria, ento, ter desaparecido. P
que os compostos presentes nos seres vivos
esmagadora maioria, o elemento carbono, e s
qumicos preferiram manter a diviso, defini
qumica dos compostos de carbono.
Devemos fazer algumas reflexe
possamos nos sentir vontade no desenvolvime
primeira vista,Esquema
a diviso
entre
qumica
orgnica e qumica
1.1.1.
Sntese
de Whler
ia, ento, ter desaparecido. Por qual razo no aconteceu isso? Ocorre
ra vista, a diviso entre qumica orgnica e qumica
os presentes nos seres vivos, se excluirmos a gua, contm, na sua
o, ter desaparecido. Por qual razo no aconteceu isso? Ocorre
Friedrich Whler, 1800 1882, qumico alemo que
(orgnica) total. Whler deu tambm importan
ria, o elemento carbono, e so extraordinariamente numerosos. Por isso sntese
os
isomerismo. Fez alguns trabalhos em colaborao com J
entes nos seres vivos, se excluirmos a gua, contm, na sua
am manter a diviso, definindo agora a qumica orgnica como a
emento carbono, e so extraordinariamente numerosos. Por isso os
postos de carbono.
nter a diviso, definindo agora a qumica orgnica como a
evemos fazer algumas reflexes sobre essas divises e definies para que
de carbono.
tir vontade no desenvolvimento de nossos estudos:
fazer algumas reflexes sobre essas divises e definies para que
1
1.1 We Are Stardust

Some 14.5 billion years ago the big bang
formed hydrogen
helium, the lightest
eleIntroduo
sand
molculas
orgnicas
ments. Further nuclear reactions in stars transmuted these elements into heavier ones, including carbon, nitrogen, oxygen, sulfur, phosphorus, and most others in the periodic table.
Massive explosions called supernovae scattered the elements in the universe, and over time
heavy elements coalesced to form planets and other celestial bodies. Through processes not
understood but about which there continues to be much research, simple molecules formed,
A qumica orgnica
o estudo dos compostos
de carbono.
eventually including organic molecules that could support
nucleic acids that make
1 lifethe
Quase todas up
asDNA
molculas
que
tornam
a
vida
possvel
contm
and RNA, the amino acids
comprise proteins, carbohydratescarbono.
such as glucose,
ThethatBasics
and other types of molecules. It is from elegant molecular building blocks like these that
Bonding
and Molecular
Structure
the incredible richness
of chemistry
and life has
evolved. So, in the truest sense we living
creatures are composed of stardust, and without supernovae not only would there be no
organic chemistry, there would be no life.
solom_c01_001-052hr1.qxd
14-10-2009
14:20
Page 1
1.1A Development of the Science of Organic Chemistry
An RNA molecule
OH
O
O
C
C
HO
CH
CH9CH2OH
C
OH
Vitamin C
The science of organic chemistry began to flower with the demise of a nineteenth century
theory called vitalism. According to vitalism, organic compounds were only those that came
from living organisms, and only living things could synthesize organic compounds through
intervention of a vital force. Inorganic compounds were considered those compounds that
came from nonliving sources. Friedrich Whler, however, discovered in 1828 that an organic
compound called urea (a constituent of urine) could be made by evaporating an aqueous
solution of the inorganic compound ammonium cyanate. With this discovery, the synthesis of an organic compound, began the evolution of organic chemistry as a scientific
discipline.
Organic chemistry is a part of our lives at every moment. Organic molecules comprise the tissue of plants as
mighty as the redwoods, convey signals from one neuron to the next in animals, store the genetic information
of life, and are the food we eat each day. The growth of living things from microbes to elephants rests on organic
reactions, and organic reactions provide the energy that drives our muscles and our thought processes.
heat
Our lives depend on organic chemistry in many other ways!
as well. Every
" article of clothing we wear is a
product of organic chemistry, whether the fibers are natural or4synthetic. Hardly a minute goes by when were
not using something made of organic molecules, such as a pen, a computer keyboard, a music player, or a cel2
lular phone. We view display screens made of organic liquid crystal arrays. Natural organic polymers comprise
wood and the paper we read. Natural and synthetic organic molecules enhance our health. There is not a single aspect of our lives that is not in some way dependent on organic chemistry. But what is organic chemistry?
NH NCO
Ammonium cyanate
HN
NH2
Urea
Organic chemistry is the chemistry of compounds that contain the element carbon.
Despite the demise of vitalism in science, the word organic is still used today by some
people to mean coming from living organisms as in the terms organic vitamins and
organic fertilizers. The commonly used term organic1 food means that the food was
grown without the use of synthetic fertilizers and pesticides. An organic vitamin means
to these people that the vitamin was isolated from a natural source and not synthesized by
a chemist. While there are sound arguments to be made against using food contaminated
Clearly, carbon compounds are central to life on this planet. Carbon as an element, however, has its origin
elsewhere.
O carbono no libera nem aceita eltrons prontamente.
View Article Online
NPR
Review
O carbono compartilha eltrons com outros tomos de
carbono bem como com diferentes tipos de tomos.
Marine natural products - Natural Product Reports (RSC Publishin...
bolomics,65 techniques
gi66 and a commentary
discovery.67
ms and
arine microorganisms
ural products research
umber of compounds
g a 30% increase from
mpounds described in
tures of the named
http://pubs
View Article Online
Review
Quando estudamos qumica orgnica, avaliamos como as
substncias orgnicas reagem.
Ligao qumica eltrons atmos
Estrutura atmica
Um tomo consiste de um ncleo denso (nutrons e
prtons), positivamente carregado e de eltrons

negativamente carregados.
Os eltrons so descritos por funes de onda orbitais
atmicos.
nuvem de densidade varivel; uma maior densidade da nuvem

probabilidade de encontrar oEstrutura
eltron naquele
ponto. Essa n
atmica
nada material; ela apenas um grfico tridimensional da pr
eltron num dado ponto. Se estivermos examinando um de
com uma certa densidade (correspondendo a uma certa pr
examinar os pontos vizinhos a este, verificamos que a pr
densidade) varia na maioria das direes; em algumas dire
a regio do espao em torno permanece
do ncleoconstante.
onde Amais
provvel
sede mesma probab
coleo
de pontos
encontrar um eltron.
definida (chamada, s vezes, de iso-superfcie), que geralmente
para representar o orbital.
Orbital atmico
Onde a nuvem tem maior densidade a

probabilidade de encontrar o eltron maior
Curva indicando a p
eltron, vlida par
Supe
const
para
Fatia do orbital 1s cortada no plano xy
Figura 1.2.4. Visualizao do orbital
Observao: a curva e a nuvem de pontos apresentadas na figura aci
Probability
Probabilit
1s
2s
3s
Estrutura atmica- Orbital atmico
0 1 2 3 4 5 6 7 8 9 10
Distance from the nucleus, r ()
1s
0 1 2 3 4 5 6 7 8 9 10
2s
0 1 2 3 4 5 6 7 8 9 10
3s
" FIGURE 6.18 Radial probability distributions for the 1s, 2s, and 3s orbitals of
hydrogen. These graphs of the radial probability function plot probability of finding the electron
as a function of distance from the nucleus. As n increases, the most likely distance at which to
find the electron (the highest peak) moves farther from the nucleus.
Os nmeros qunticos so usados para descrever um
orbital:
Comparing the radial probability distributions for the 1s, 2s, and 3s orbitals reveals
three trends:
Nmero quntico principal

(n): define o tamanho relativo dos
1. The number of peaks increases with increasing n, with the outermost peak being
larger than
inner ones. 1, 2, 3
orbitais, pode ter valores
inteiros
2. The number of nodes increases with increasing n.
3. The electron density
more spread
out with increasingmaior
n.
medida que n aumenta,
o becomes
orbital
torna-se
e o eltron
One widely used method of representing orbital shape is to draw a boundary surpassa mais tempo mais
distante
do portion,
ncleo.
Especifica
o thenvel de
face that encloses
some substantial
say 90%, of
the electron density for
orbital. This type of drawing is called a contour representation, and the contour repreenergia.
sentations for the s orbitals are spheres ( FIGURE 6.19). All the orbitals have the same
!
shape, but they differ in size, becoming larger as n increases, reflecting the fact that the
electron density becomes more spread out as n increases. Although the details of how
1s
(a)
(b)
2s
3s
# FIGURE 6.19 Comparison of the 1s,

2s, and 3s orbitals. (a) Electron-density
distribution of a 1s orbital. (b) Contour
representions of the 1s, 2s, and 3s orbitals.
Each sphere is centered on the atoms
nucleus and encloses the volume in which
there is a 90% probability of finding the
electron.
Estrutura atmica- Orbital atmico
O nmero quntico secundrio ou azimuthal (l). Refere-se ao
formatos dos orbitais.

Os eltrons em uma determinada camada podem ser agrupados em
subcamadas.
O valor de l designado pelas letras s, p, d, f,
O nmero quntico magntico (ml). Esse nmero quntico
fornece a orientao do orbital no espao.
(Aufbau is German for building up.)

2. Pauli exclusion
principle:
A maximum
of two electrons may
Estrutura
atmicaOrbital atmico
but only when the spins of the electrons are paired. An elec
axis. For reasons that we cannot develop here, an electron i
the other of just two possible spin orientations. We usually
Configurao eletrnica
by arrows, either k or j. Thus two spin-paired electrons w
Unpaired
electrons,
which que
are not
permitted
Os princpios a seguir so usados
para
determinar
orbitais
os in the same o
eltrons ocupam:
(or jj).
O princpio de aufbau: um
eltron rule:
sempre
parato um
orbital
3. Hunds
When vai
we come
orbitals
of equal energy (d
disponvel de menor energia;
as the three p orbitals, we add one electron to each with th
O princpio da excluso de Pauli:
each of the degenerate orbitals contains one electron. (This all
No mais que dois eltrons podem ocupar cada orbital
repel each other, to be farther apart.) Then we begin adding a
Os dois eltrons tem que ter spins oposttos;
degenerate orbital so that the spins are paired.
A regra de Hund determina que, quando h orbitais degenerados
(orbitais de mesma energia), If

um
vai rules
ocupar
orbital
vazio
antes elements of th
weeltron
apply these
to some
of the
second-row
de ser emparelhado com outro
eltron.
the results
shown in Fig. 1.7.
2p
Energy
2p
2p
2s
2s
2s
1s
Boron
1s
Carbon
1s
Nitrogen
Figure 1.7 The ground state electron configurations of some second-row
O estudante certamente j conhece a seqncia de preenchimento dos

nveis de energia, que pode ser lembrada pela figura 1.2.5. Esta regra s vezes chamada
Estrutura
atmica
de Princpio da Construo; em ingls usa-se uma
curiosa expresso
mista: Aufbau
Principle, sendo que Aufbau uma palavra alem que significa construo, estrutura,
EXERCCIO
etc. Alguns definem o Aufbau Principle simplesmente como a seguinte regra: orbitais
de menor energia devem ser preenchidos primeiro. Outros do significado muito mais
Escreva a configurao eletrncia do estado fundamental de cada
amplo, dizendo que Aufbau Principle o princpio da construo terica da tabela
um dos seguintes elementos:
peridica dos elementos atravs da distribuio apropriada dos eltrons nos tomos,
incorporando neste princpio o princpio de excluso de Pauli e a regra de Hund (veja
adiante). A regra dada pela figura, porm, simplesmente uma maneira prtica (e fcil de
Nitrognio (nmero atmico
lembrar) 7)
para colocar os vrios orbitais em ordem de energia crescente. interessante
observar
Oxignio (nmero atmico
8)que h umas poucas excees a esta regra (veja cromo e cobre).
Flor (nmero atmico 9)

1s
2s
2p
3s
3p
3d
4s
4p
4d
4f
5s
5p
5d
5f
Figura 1.2.5. Seqncia de preenchimento de orbitais
H ainda a considerar que dentro de um mesmo sub-nvel com vrios

orbitais de mesma energia (por exemplo, no sub-nvel 2p, em que h trs orbitais com a
mesma energia, px, py e pz) os eltrons tendem a possuir o mesmo spin e a se localizarem
Energy
lent bond,
oxygen
always
has two
covalent
bonds,
nitroge
xygen always
has two covalent
bonds,paired.
nitrogen always
has three
covalent
degenerate orbital
so that
thecarbon
spins are has
orgnica
os that
elementos
quefor
aparecem
com the
maior
freq
bonds,
and
four
covalent
bonds.
Notice
(except
hydrogen)
sum
s.arbon
Notice
forbonds.
hydrogen)
thethat
sum(except
bonds,
and apenas
carbon
has
four
covalent
bonds.
Notice
that
(ef
hasthat
four(except
covalent
Notice
for hydrogen)
the
sum
nos
dois
primeiros
nveis
principais;
por
isso
If we apply theseofrules
to
some
of
the
second-row
elements
of
the
periodic
table,
we
get
the number
of
bonds
pairs
is four:of
The
halogens,
with
oneisbond,
havehalogen
three
our:
with
have
threeand lone
of the
number
bonds
and lone
pairs
four: The
er ofThe
bonds
and
lone
four: The
halogens,
with
one
bond,
have
three
Estrutura
atmica
the halogens,
results
shown
in pairs
Fig.one
1.7.isbond,
nesses
nveis.
lone has
pairs;
withand
twonitrogen,
bonds,
has
two
lonebonds,
pairs;
andbonds,
nitrogen,
three
bonds,an
o lone pairs;
andbonds,
nitrogen,
with
three
bonds,
lone pairs;
oxygen,
with Cada
two
haswith
two
lone pairs;
xygen,
with two
twooxygen,
lone pairs;
with
three
orbital pode
acomodar
1 ou 2 e
has
one
lone
pair.
Atoms
that
have
more
bonds
or
fewer
bonds
than
the
number
reor fewer
than
the
number
rehas
one
lone
pair.
Atoms
that
have
more
bonds
or
fewer
ebonds
pair. Atoms
thatbonds
have
more
bonds
or
fewer
bonds
than
the
number
reque
ter
spins
opostos.
Isto
porque,
de
acordo
com
2p
2p
2p
2p
2p
2p
quired
for
a
neutral
atom
will
have
either
a
formal
charge
or
an
unpaired
electron.
rneutral
a formal
charge
an either
unpaired
electron.
de atom
um mesmo
podem
ter todos
os
for aeltrons
neutral
will tomo
have no
either
a formal
char
atom
will or
have
a formal
charge quired
or an unpaired
electron.
numbers
are
veryyou
important
remember
you are
first
2s
2s structures
2sare
2sThese
simbologia
muito structures
utilizada
pa
ember
you are
first
drawing
These
numbers
arewhen
very2sUma
important
to2sdrawing
remember
when you
ers arewhen
very important
to remember
when
firsttodrawing
structures
of
organic
compounds
because
they
provide
ayou
quick
way
to recognize
you have
eltrons
em
um
tomo
consiste
emwhen
representar
cada
de a quick because
way to 1srecognize
when
you
have
of
organic
compounds
because
they
provide
a
quick
wayo
ompounds
they
provide
a
quick
way
to
recognize
when
have
1s
1s
1s
1s
1s
made a mistake.
identificando
o orbital pelo
nmero quntico princi
Neon
Carbon
Fluorine
Boron
Nitrogen made aOxygen
mistake.
ake.
nmero quntico secundrio, com ndices (x, y, z, etc

Cl
Figure 1.7 The ground state electron configurations ofFsome second-row
elements. valor do nmero quntico magntico; o nmero de
F
Cl
F NCl
H
O
C
N
O C
N
HC
O
N
aparece como expoente; por exemplo:
Br
I
Br
Br
I
1.11 IMolecular
Orbitals
one
bond
one
bond
two
bonds
three
bonds
four bonds
1
onds
three
bonds
four
bonds
bond
one bond
two
bonds
three bonds
four
onebonds
bond Hidrognio:
one bond1s
two bonds
three b
Atomic orbitals provide a means for understanding how atoms form covalent bonds. Let
1
1
2
2
Carbono:
1s
2s
2p
2p
2 2s2 2p2
x
y
2
2
3
2C:
1s
2
2
4
1sa bond
2s between
2pfor
us consider a very
caseformation
of
two
hydrogen
atoms
formO, CO
6 simple
2p 3 ,toCH
27N:
O
,,2sHNO
,1sand
,1 notice
In
the
Lewis
structures
2- CH
1
1that each
2
8O:21s
2
2each for
3 CH
O3 ,structures
CH
O,
CO
,
N
,
and
notice
that
each
Nitrognio:
CH
O
,
HNO
,
CH
O,
CO
,
N
O22N2p
,2HNO
, CH
wis
for
and
notice
that
In
the
Lewis
structures
2
3
2
x 2py 32p
z
2(Fig.2 1.8).
3
2
3
2
22s
2O, CO
a hydrogen
molecule
2
1
1
2
2
atomatoms
hasare
ashell)
complete
octet
hydrogen,
which
has (except
a filled
outer
shell)
and that
Oxignio:
1s 2shydrogen,
2px 2p
gen,
which
has
ahydrogen
filled
outer
andfarthat
When
two(except
relatively
apart
total energy
isashell)
simply
that
ofthat
y 2pwhich
z
complete
octet
hydrogen,
which
has their
a (except
filled
outer
and
atom
has
complete
octet
has
each
atom
has the
formal
(Inappropriate
the
Lewis
structure
a
two
isolated
hydrogen
atoms
(I).
Formation
a covalent
reduces
thecharge.
overall
energy
arge.
drawing
the
Lewis
structure
for
a bond
as the(In
appropriate
formal
charge.
(Inofappropriate
drawing
the
Lewis
structure
fordrawing
a
each
atom
has the
formal
charge.
(In for
drawin
compound
that
has
two oxygenoxygen
or more
oxygensingle
atoms,
avoid
single avoid
bonds.ox
atoms,
single
bonds.
hat
has avoid
two oroxygenoxygen
more
oxygen atoms,
avoid
compound
that
hasbonds.
two oroxygenoxygen
more oxygen atoms,
are weak
bonds,
and few
compounds
have
them.)
ds
them.)
1.2.
Orbitais
Atmicos
e Moleculares
Ligao Qumica
eakhave
bonds,
and fewThese
compounds
have
them.)
These
are
weak
bonds,
and
few compounds
have them.)
IV
I
OO
H OOCNOO
+
Energy
OO
HCCOHH
Nuclear
repulsionO
No attraction
O
H CC
OH
N
NH
H
O
O
H O N O
O C O+
O
O
HCH
NH N
COH
O
O
OCO
HONO
+
O
NH CN H
III
O nmero de Covalent
ligaes covalentes que um tomo forma depende tanto do nmero de
1
A
pair
of
shared
electrons
can
also
shown
as
aque
lineelebetween
atoms.
Compare
bonding
436A
kilojoules
mol
own
a line eltrons
between
atoms.
Compare
detwo
valncia
quanto
doII nmero
adicional
de
eltrons
necessita
para
atingiras a line be
ared as
electrons
can also
be
shown
as
a line
between
twobe
Compare
pair
ofatoms.
shared
electrons
can
alsotwo
be
shown
thefollowing
preceding
structures
with the
Attraction between
a configurao
de gs
nobre.
g ones:
structures with
the
ones:
the following
preceding ones:
structures with the following ones:
electrons and nuclei
r = 0.74
Figure 1.8 The potential energy of the
No segundo nvel h um orbital 2s e trs orbitais 2p: 2px, 2py e 2pz. Todos
atmicaOrbital
os orbitais s tm forma esfrica, sendoEstrutura
maiores (maior
raio da esfera)
para atmico
nveis mais
elevados; no tm, entretanto, exatamente a mesma forma quando examinados como um
corte porque os orbitais dos nveis superiores tm mais ns. Um n uma regio do
espao (pode ser uma superfcie, um plano, uma reta, um ponto) onde a probabilidade de
encontrar o eltron nula e onde ocorre inverso de fase da onda; maioresNode
detalhamentos
2
2
2
2
Radialfora
probability
function = objetivos
4pr [c(r)] presentes. cO
c2s
c3s2
deste aspecto esto
de nossos
apenas lembrar-se
1s estudante deve
Thus, the plots of radial probability function in Figure 6.18 are
que orbitais
s so todos esfricos quando vistos por fora, e tm maior tamanho para
equal to the plots of [c(r)]2 in Figure 6.21 multiplied by 4pr 2. The
fact that
increases
rapidly (maior
as we movevalor
away from
4pr 2 de
nveis mais
altos
energia
dethen).nucleus
r
r
r
hydrogen atom. You will notice that these plots look distinctly different from the radial probability functions shown in Figure 6.18.
As shown in Figure 6.20, the collection of points a distance r
from the nucleus is the surface of a sphere of radius r. The probability density at each point on that spherical surface is [c(r)]2. To add
up all the individual probability densities requires calculus and so is
beyond the scope of this text. However, the result of that calculation
tells us that the radial probability function is the probability density,
[c(r)]2, multiplied by the surface area of the sphere, 4pr 2:
Nodes
Os orbitais atmicos so designados pelas letras s, p d
e f.
makes the two sets of plots look very different from each other. For
example, the plot of [c(r)]2 for the 3s orbital in Figure 6.21 shows
that the function generally gets smaller the farther we go from the
nucleus. But when we multiply by 4pr 2, we see peaks that get larger
and larger as we move away from the nucleus (Figure 6.18).
The radial probability functions in Figure 6.18 provide us with
the more useful information because they tell us the probability of
finding the electron at all points a distance r from the nucleus, not
just one particular point.
Orbitais s
n ! 1, l ! 0
1s
n ! 2, l ! 0
2s
n ! 3, l ! 0
3s
! FIGURE 6.21 Probability density [C(r )] 2 in the 1s, 2s, and 3s

orbitals of hydrogen.
RELATED EXERCISES: 6.50, 6.59, 6.60, and 6.91
1s
2s
GO FIGURE
3s
(a) Note on the left that the color is deep pink in the interior of each lobe
but fades to pale pink at the edges. What does this change in color repreFigura
1.2.6.
Orbitais
s aligned
de camadas
sent? (b) What label
is applied
to the
2p orbital
along thediferentes
x axis?
z
z
J os orbitais 2p
tm forma de
haltere, comz dois lobos situados de lados
opostos do ncleo do tomo, cada um deles tendo a forma exata da imagem no espelho
do outro. O plano que passa pelo centro do ncleo do tomo em posio perpendicular
ao eixo xdo orbital y2p (ox mesmo plano
que seria yo espelho
referido acima) um plano
y x
x
y
nodal, onde a probabilidade de encontrar o eltron nula, e onde ocorre
inverso
de
" FIGUREa6.22
The p orbitals.
(a) Electron-density distribution of a 2p orbital.
fase da onda.
pz
px
py
(b) Contour representations of the three p
z
Orbitais p
(a)
(b)
z
Estes so os orbitais mais importantes em qumica
orgnica
plano nodal
The d and f Orbitals
When n is 3 or greater, we encounter the d orbitals (for which l = 2). There are five 3d
orbitals, five 4d orbitals, and so forth because in each shell there are five possible values
orbitals. The subscript on the orbital label

indicates the axis along which the orbital lies.
Ligaes Qumicas
Uma ligao qumica uma unio entre tomos e
atravs dela que muitas das propriedades das

substncias so entendidas;
Liberao de energia e
Aumento da estabilidade do sistema;
UM ELETRLITO
UM NO ELETRLITO
Ligaes Qumicas
Lewis mostrou que a falta de reatividade dos gases
nobres (grupo 8 A) indica um alto grau de estabilidade em

suas configuraes eletrnicas.
ximum of two electrons may be placed in each orbital

ectrons are paired. An electron spins about its own
develop here, an electron is permitted only one or
in orientations. We usually show these orientations
two spin-paired electrons would be designated il.
ot permitted in the same orbital, are designated kk
the
hydrogen
atom somewhat
gives
it a partial
positive
c
large,
the electrons
are notelectron
shareddeficient
equallyand
and
a polar
covalent
bon
The chlorine atom becomes somewhat electron rich and bears a partial negative c
Remember: One definition of electronegativity

is the ability of an
&!
&"
electrons
that it is Qumicas
sharing in a covalent
bond.
H CC
a lC
Ligaes
orbitals of equal energy (degenerate orbitals) such
one An
electron
to each withthe
theirof
spins
unpairedauntil
example
such
polar
covalent
bond
the onepositive
in hydrogen
Because
hydrogen
chloride
molecule
has aispartially
end andchlori
a par
ntains one electron. (This allows the electrons, which
adding
A ittendncia
os ittomos
reagirem
modo aelectrons
formar closer t
end,
is a electron
dipole,
and
has a dipole
art.)
Thentive
we
begin
agreater
second
tode
each
tom,
with
its
electronegativity,
pullsmoment.
thedebonding
ns are paired.
uma
camada
externa
(valncia)
com
8beeltrons
valncia
The
direction
of
polarity
of
a
polar
bond
can
symbolized
by
a
vector
quanti
he
hydrogen
somewhat
electron
deficient
and
gives
it
a
partial
posit
he second-row
elements ofatom
the periodic
table, we get
chamada
de
Regra
do
octeto.
The crossed
endbecomes
of the arrow
is the positive
end rich
and the
is the negativ
The chlorine
atom
somewhat
electron
andarrowhead
bears a partial
negat
!
2p
199: (negative end)

(positive
end)
&
&"
2p !
2p
2p
2p
In HCl
, for example,
we would
indicate
theCdirection
of the dipole moment in
H
C
a lC
2s
2s
2s
2s
H 2O
ing way:
1s
1s
1s
1s
Because the hydrogen chloride molecule has

a partially positive end and
H 9 Cl
ve end, itis
dipole,
it has de
a dipole
moment.
199:
Hadois
tiposand
principais
ligaes:
The direction
ofmoment
polarity
polar
bond
can
be
symbolized
by
a
vector
q
Ligao
inica isofa aphysical
The dipole
property
that
can
be
measured
experime
1.11 Molecular Orbitals
covalente
The
crossed
ofproduct
the
arrow
is the
positiveofend
theinarrowhead
the ne
defined end
asLigao
the
of the
magnitude
the and
charge
electrostaticis units
(e
understanding how atoms form covalent bonds. Let
tion of a distance
bond between two
hydrogen
atoms to form
that
separates
them
in centimeters
(cm): (negative end)
(positive
end) 199:
Nitrogen
Oxygen
Fluorine
Neon
figurations of some second-row elements.
Dipole moment $ charge (in esu) # distance (in cm)

we would indicate the direction of the dipole mome
%$e#d
atively far apart their total energy is simply that of

mation of a covalent bond reduces the overall energy
n HCl, for example,

ng way:
Ligao Inica
formada quando um ou mais eltrons so tranferidos de um
tomo para outro, criando ons positivos (ctions) e negativos

(nions).

Na
Cl
Na
ATRAO ELETROSTTICA
Cl
Ligao covalente
Envolve o compartilhamento de eltrons de valncia entre tomos.
Section 1.4
Representation of Structure
13
SOLVED
Ligaes covalente
artial negative charge on the oxygen atom in a C O bond. The bond

and the bond dipole moment is 2.30 D.
there were a full negative charge on the oxygen atom, the dipole moment
Estrutura de Lewis
10-10 esu211.22 * 10-8 cm2 = 5.86 * 10-18 esu cm = 5.86 D
dipole moment is 2.30 D, we calculate that the partial negative charge on

is about 0.4:
2.30
= 0.39
5.86
Um modo simples para indicar as ligaes covalentes em
molculas usar o que chamamos de Estrutura de

ou estruturas de pontos.
compounds (for example, HLewis
C OH ).
c. H C NH
e. HO Br
g. I Cl
A
regra
do
d. H C Cl
f. H C MgBr
h.octeto
H N OH deve ser obdecida.
d + and d - to show the direction of polarity of the indicated bond in each

+
3
esentation of Structure
res
mbols we have been using, in which the valence electrons are repree called Lewis structures. Lewis structures are useful because they
oms are bonded together and tell us whether any atoms possess lonehave a formal charge.
ctures for H 2O, H 3O +, HO -, and H 2O2 are shown below.
lone-pair electrons
H+
HOH
hydronium ion
HO
hydroxide ion
HOOH
hydrogen peroxide
w a Lewis structure, make sure that hydrogen atoms are surroundan two electrons and that C, O, N, and halogen (F, Cl, Br, I) atoms
y no more than eight electronsthey must obey the octet rule. Vaot used in bonding are called nonbonding electrons or lone-pair
s and the electrons are in place, each atom must be examined to see
American chemist Gilbert Newton

Lewis (18751946) was born in
Weymouth, Massachusetts, and received a Ph.D. from Harvard in
1899. He was the first person to prepare heavy water, which has deu-
Ligaes covalente
Estrutura de Lewis
1) Uma ligao simples representada por uma linha entre dois
elementos qumicos.
2) Um par de eltrons no-ligantes representado por dois
pontos.
hydrogen
ion
hydride
ion
hydrogen
bromide
bromineSection
chlorine
1.4 Representation
of Structure
In studying
the molecules
in thisbromine
section,
notice
that when
the atoms
radical
ionor an unpaired
radicalelectron, hydrogen and the halogens each ha
formal charge
Ligaes covalente
lent
bond,
oxygen
always
has
two
covalent
bonds, nitrogen always has th
H
H
Br
Br
Br Br
Cl Cl
In studying the molecules inbonds,
this section,
notice
when
the atoms
bear
a (except for hydro
and carbon
hasthat
four
covalent
bonds.dont
Notice
that
Section
1.4
Representation
of
Structure
15
hydride
hydrogen
bromide
bromine andbromine
chlorine
formal charge
or an unpaired
electron,
hydrogen
the
halogens
each
have
one
covaion
radical
ionof the number
radicalof bonds and lone pairs is four: The halogens, with one bon
lent bond, oxygen always has two
covalent
bonds, with
nitrogen
alwayshas
hastwo
three
covalent
lone
pairs;
oxygen,
two
bonds,
lone
pairs; and nitrogen, with
BrO has
nmero
de
ligaes
covalentes
que
umbonds
tomo
forma
H
Brlone
BrNotice
Cl Cl(except
bonds,
and carbon
fourBr
covalent
bonds.
that
for
hydrogen)
theorsum
has one
pair.
Atoms
that
have
more
fewer
bonds than the
g of
thethe
molecules
in
this
section,
notice
that
when
the
atoms
dont
bear
a
ofdepende
bonds and
lone
pairs
is
four:
The halogens,
with
one
bond,
three
hydrogen number
bromide
bromine
bromine
chlorine
tanto
do
de
eltrons
de
valncia
quanto
quired
fornmero
a neutral
atom
will
have
either
ahave
formal
charge or an unpai
eradical
or
an
unpaired
electron,
hydrogen
and
the
halogens
each
have
one
covaion with two
radical
lone pairs; oxygen,
bonds,
has
two lone
and
nitrogen,
with
three bonds,
These
numbers
arepairs;
very
important
toele
remember
when you
are first drawi
do
nmero
adicional
de
eltrons
que
necessita
para
xygen
always
has
two
covalent
bonds,
nitrogen
always
has
three
covalent
has one lone pair. Atoms that have
more compounds
bonds or fewer
bonds
than
the number
reof
organic
because
they
provide
a
quick
way to recognize wh
arbon
has
four
covalent
bonds.
Notice
that
(except
for
hydrogen)
the
sum
atingir
a
configurao
de
gs
nobre.
es quired
in this for
section,
notice
that will
when
the aeither
atoms
bearcharge
a
a neutral
atom
have
adont
formal
or an unpaired electron.
made
mistake.
rd of
bonds
and
lone
pairs
is
four:
The
halogens,
with
one
bond,
have
electron,
hydrogen
halogenstoeach
have one
covaThese
numbers
are and
verythe
important
remember
when
you are firstthree
drawing structures
xygen,
with
two
bonds,
has
two
lone
pairs;
and
nitrogen,
with
three
bonds,
hasoftwo
covalent
bonds, nitrogen
has three
covalent
F toClrecognize when you have
organic
compounds
becausealways
they provide
a quick
way
H
O
N
C
pair.
Atoms
that
haveligao
more
bonds for
or fewer
bonds
uma
P E R I O Dthe
I C than
T Asum
B L E the
O F T H number
E E L E M E N T S recovalent
Notice
that (except
hydrogen)
made
a bonds.
mistake.
Br electron.
I
neutral
atom
will The
havehalogens,
either a with
formal
anthree
unpaired
lone pairs
is four:
onecharge
bond, or
have
one bond
two bonds
three bonds
four b
ers
are very
toFremember
whenone
youbond
are
first
drawing
structures
HCl nitrogen,
He
o bonds,
hasimportant
two
lone
pairs;
and
with
three
bonds,
C
H
O to recognize
N
C
duas
ligaes
ompounds
because
they
provide
a
quick
way
when
you
have
hat have more bonds or Ifewer
bonds
than
the number
re- for CH O B, HNO
2LIBr Be
N3 , CH
O
FO,Ne
C
CO
, and N2 , not
In
the
Lewis
structures
2
2
2
3
ake.
will have one
either
a formalone
charge
or antwo
unpaired
electron.
bond
bondatom
bonds
three
four bondswhich has a filled outer sh
has
a complete
octetbonds
(except hydrogen,
Mg first drawing structures
Na are
P
S
Cl Ar
Si
Al
portant toFremember
when you
each atom has the appropriate
formal
charge.
(In
drawing the Lewis st
Cl
2O
N
C
ause they
provide
a
quick
way
to
recognize
when
you
have
trs
ligaes
CH
CONi
, and NGa2 , notice
In the Lewis structures for
that Breach
2O2Ti, HNO
3 , CH
3 more
has2FeO,
two
Cacompound
K
Sc
Mn
Co or
Cu Znoxygen
V that
Cr
As Se avoid
Ge atoms,
Kr oxygenoxygen s
Br
I
atom has a complete octet (except
hydrogen,
which
has
a few
filled
outer shell)
andthem.)
that
These
are
weak
bonds,
and
compounds
have
ond
one bond
two bonds
three
bonds Ru four
bonds Cd In Sn Sb Te I Xe
Rb Sr formal
Y
Rh Pd Ag
Zr charge.
Nb Mo Tc
each atom
has the appropriate
(In drawing
the Lewis structure for a
Cl
O bonds.
O
O
O
compoundOthat has two or Nmore oxygen atoms,
avoid oxygenoxygen
single
C2Ba
Cs
*La
Re
Os
Ir
Pt
Au
Hf
Ta
W
Hg
Bi
Po
At
Pb
Tl
Rn
quatro
ligaes
HNO
,Oand
N2 , notice
wisThese
structures
for CH
that each H C H
2O2 , and
3 , CH
2O, CO
Hthem.)
are weak
bonds,
few
compounds
H3 Chave
HONO
OCO
N
Br
+ and that
omplete
octet
(except
hydrogen,
which
has
a
filled
outer
shell)
bond
two bonds
threeFrbonds
Ra #Ac Rf four
Sg Bh Hs Mt Uun Uuu Uub
Db bonds
Uuq
as the appropriate
formal
charge.
(In
drawing
the
Lewis
structure
for
a
O
O
O
O
Estrutura de Lewis
solom_ep_F01-F02v1.qxd
1
IA
18
VIIIA
2
IIA
Lithium
6.941
15
VA
16
VIA
17
VIIA
Helium
4.0026
10
Berylium
9.0122
Boron
10.811
Carbon
12.011
Nitrogen
14.007
Oxygen
15.999
Fluorine
18.998
Neon
20.180
11
12
13
14
15
16
17
18
Sodium
22,990
Magnesium
24.305
3
IIIB
4
IVB
5
VB
6
VIB
7
VIIB
8
VIIIB
9
VIIIB
10
VIIIB
11
IB
12
IIB
Aluminum
26.982
Silicon
28.086
Phosphorus
30.974
Sulfur
32.065
Chlorine
35.453
Argon
39.948
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Potassium
39.098
Calcium
40.078
Scandium
44.956
Titanium
47.867
Vanadium
50.942
Chromium
51.996
Manganese
54.938
Iron
55.845
Cobalt
58.933
Nickel
58.693
Copper
63.546
Zinc
65.409
Gallium
69.723
Germanium
72.64
Arsenic
74.922
Selenium
78.96
Bromine
79.904
Krypton
83.798
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Rubidium
85.468
Strontium
87.62
Yttrium
88.906
Zirconium
91.224
Niobium
92.906
55
56
57
72
Caesium
132.91
Barium
137.33
Lanthanum
138.91
87
88
Francium
(223)
Radium
(226)
95.94
(98)
Ruthenium
101.07
Rhodium
102.91
Palladium
106.42
Silver
107.87
Cadmium
112.41
Indium
114.82
Tin
118.71
Antimony
121.76
Tellurium
127.60
Iodine
126.90
Xeno
131.29
73
74
75
76
77
78
79
80
81
82
83
84
85
86
Hafnium
178.49
Tantalum
180.95
Tungsten
183.84
Rhenium
186.21
Osmium
190.23
Iridium
192.22
Platinum
195.08
Gold
196.97
Mercury
200.59
Thallium
204.38
Lead
207.2
Bismuth
208.98
Polonium
(209)
Astatine
(210)
Radon
(222)
89
104
105
106
107
108
109
110
111
112
114
Actinium
(227)
Rutherfordium
(261)
Dubnium
(262)
Seaborgium
(266)
Bohrium
(264)
Hassium
(277)
Meitnerium
(268)
(281)
(272)
(285)
(289)
58
59
60
61
62
63
64
65
69
70
71
Molybdenum Technetium
66
67
68
Page 2
14
IVA
IUPAC recommendations:
Chemical Abstracts Service group notation :
Carbon
12.011
SOLOMONS
13
IIIA
Symbol :
Name (IUPAC) :
Atomic mass :
12:00
Hydrogen
1.0079
2-10-2009
Atomic number:
Ligaes covalente
Como desenhar as estruturas de Lewis.
Ligaes covalente
Carga formal
Uma vez que os tomos e eltrons esto no lugar, cada
tomo deve ser examinado para ver quando uma carga

pode ser designada para ele.
Uma carga positiva ou negativa designada a um tomo
chamada carga formal.
Carga formal =
N de eltrons
de valncia do
tomo livre
N de eltrons
no-ligantes
do tomo no
composto
- 1
2
N de eltrons
das ligaes que
o tomo realiza
Ligaes covalente
Carga formal
Ligaes covalente
Ressonncia
Muitas vezes, mais de uma estrutura de Lewis
equivalente pode ser escrita para uma molcula ou on.
Cada uma delas tem a configurao de um gs nobre

Pode-se converter uma estrutura em qualquer outra
trocando apenas a posio dos eltrons.
Ligaes covalente
Ressonncia
A teoria da ressonncia afirma que sempre que uma ou
um on puder ser representada por duas ou mais

estruturas de Lewis, que diferem somente nas posies
dos eltrons, duas coisas so verdadeiras:
Nenhuma destas estruturas, ser uma representao correta para
a molcula.
A molcula ou o on ser mais bem representado por um hbrido
(mdia) destas estruturas.
resonance hybrid
Resonance contributors are shown with a double-headed arrow between them. The
double-headed
doesAbout
not mean
that the structures
in equilibrium with
one
Ligaes
P T E R 7 Electron Delocalization and Resonancearrow
More
Molecular
Orbital are
Theory
another. Rather, it indicates that the actual structure lies somewhere between the
structures of the resonance contributors. Resonance contributors are merely a converesonance structure.
actual
structure
with
delocalized
electrons
is called a
nient way to The
show the
they do
not depict
any real electron
distribution.
p electrons;
resonance hybrid.
Notice
is easyC-1
to see
there
are issixnotpaelectrons
in the
For example,
thethat
bonditbetween
and that
C-2 in
benzene
double bond,
al- ring
thoughcontributor.
the resonance contributor on the left implies that it is. Nor is it a single bond,
of each resonance
as represented by the resonance contributor on the right. Neither of the contributing
Electron delocalization is shown by
resonance structures accurately represents the structure of benzene. The actual strucdouble-headed arrows ( 4 ).
1
1
ture of benzenethe resonance hybridis given by the average of the two resonance
Equilibrium is shown by two arrows
2
2
contributors.
pointing in opposite directions ( ).
The following analogy illustrates the difference between resonance contributors and
the resonance hybrid. Imagine that you are trying to describe to a friend what a
resonance
contributor
rhinoceros
looks like.
You might tell your resonance
friend that acontributor
rhinoceros looks like a cross
between a unicorn and a dragon. The unicorn and the dragon dont really exist, so they
are like the resonance contributors. They are not in equilibrium: A rhinoceros does not
jump back and forth between the two resonance contributors, looking like a unicorn one
minute and a dragon the next. The rhinoceros is real, so it is like the resonance hybrid.
The unicorn and the dragon are simply ways to represent what the actual structurethe
resonance
hybrid like unicorns and dragons, are imagirhinoceroslooks like. Resonance
contributors,
nary, not real. Only the resonance hybrid, like the rhinoceros, is real.
Ressonncia
zation is shown by
rrows ( 4 ).
own by two arrows
site directions ( ).
double-headed arrow does not mean that the structures are in equilibrium with one
another. Rather, it indicates that the actual structure lies somewhere between the
structures of the resonance contributors. Resonance contributors are merely a convenient way to show the p electrons; they do not depict any real electron distribution.
For example, the bond between
C-1 and C-2 in benzene
is not a double bond, alunicorn
dragon
resonance contributor
though the resonance contributor on the left implies that it is. Nor is it a single bond,
as represented by the resonance contributor on the right. Neither of the contributing
resonance structures accurately represents the structure of benzene. The actual structure of benzenethe resonance hybridis given by the average of the two resonance
contributors.
rhinoceros
resonance
The following analogy illustrates the differencehybrid
between resonance contributors and
the resonance hybrid. Imagine that you are trying to describe to a friend what a
Electron delocalization occurs only if all the atoms sharing the delocalized elecrhinoceros looks
You
might
thatpaorbitals
rhinoceros
looks overlap.
like a cross
trons like.
lie in or
close
to the tell
sameyour
plane,friend
so that their
can effectively
between a unicorn
and acyclooctatetraene
dragon. The unicorn
and but
thetub
dragon
dont
really
so they
For example,
is not planar,
shaped.
Because
the pexist,
orbitals
covalente
Ligaes covalente
Ressonncia
on acetato:
O
H3C
O
H3C
H3C
O
A
O
C
on
carbonato:
O
O
O
O
O
C
O
O
C
O
Ligaes covalente
Ressonncia
CONSIDERAES SOBRE ESTRUTURAS DE RESSONNCIA:
As estruturas que possuem o maior nmero de tomos com o octeto
completo contribuem mais para o hbrido de ressonncia.
Os pares de eltrons so sempre deslocados preferencialmente na
direo dos tomos mais eletronegaGvos.
No caso de estruturas que possuem cargas opostas separadas, a
contribuio mais importante dada pelas frmulas em que a distncia
entre essas cargas a menor possvel.
No caso de ons e radicais, quanto maior o nmero de estruturas de
ressonncias, mais estvel eles sero.
Ligao covalente
As ligaes covalentes so classificadas em duas
categorias, dependendo da diferena de

eletronegatividade entre os tomos ligados.
Eletronegatividade a tendncia que um tomo tem de atrair
para si eltrons que esto sendo compartilhados.
tion of covalent bonding given previously, do you expect the H H bond

Cl
H Cl Cl H H
o be weaker or stronger than the H H bond in H2?ClH! !
Ligaes covalentes
By sharing the bonding electron pair, each chlorine atom has eight electrons (an octet)
In forming
the
covalent
bond,
each
atom
acquiresof aargon.
second electron, ach
in its
valence
shell, thus
achieving
the hydrogen
noble-gas electron
configuration
tructures
The structures shown
here for H
called either Lewis
2 and Cl2 are
stable, two-electron,
noble-gas
electron
configuration
ofstructures
helium.or
Ligao the
covalente
apolar
aquela
na
qual
os
eltrons
Lewis electron-dot structures. In writing Lewis structures, we usually show each shared
Formation
of
aascovalent
bond
between
two
atoms
tothis
give
Cl2 molecule
electron pair
a Lewis
line and any
unshared
electron
pairs Cl
as dots.
Written
way,a the
on of covalent esto
bonds can
be represented
with
symbols.
The formation
igualmente
compartilhamentos
entre
dois
tomos.
Lewis
for Hway:
2 and Cl2 are
represented
instructures
a similar
olecule from two H atoms, for example, can be represented as

H
Cl
Cl
For nonmetals, the number

electrons in a neutral
Clof valence
! Cl
Cl atom
Cl is the same as the
group number. Therefore, one might predict that 7A elements, such as F, would form
one covalent bond to achieve an octet; 6A elements, such as O, would form two covalent
5A elements, such as N, would form three; and 4A elements, such as C, would
By sharingbonds;
the
bonding electron pair, each chlorine atom has eight electrons (an
form four. These predictions are borne out in many compounds, as in, for example, the
in its valence
shell,with
thus
achieving
the noble-gas
electron
of argon.
compounds
hydrogen
of the nonmetals
of the second
row of theconfiguration
periodic table:
H ! H
H H
he covalent bond,
each hydrogen
atom acquires
a second
electron, achieving
Ligao
covalente
polar um
dos tomos
exerce maior
wo-electron, noble-gas
configuration
of helium.
atraoelectron
pelosThe
eltrons
ligantes
que
oH outro.
structures
shown
here
for
are Hcalled
2 and Cl2 can
on of a covalent bond between two Cl atoms to give a Cl2 molecule
be either Lewis structu
Lewis electron-dot structures.
In
H F
H writing
O
H Lewis
N H structures,
H C H we usually show each
in a similar way:
electron pair as a line and any unshared

as dots. Written this w
H
Helectron pairs
H
H deformao
da nuvem
and Cl2 areem direo ao elemento
Lewis structures
for H2eletrnica,
eletronegativo.
Cl mais
! Cl
Cl Cl
SAMPLE EXERCISE 8.3
Lewis Structure of a Compound
Cl
Cl
Given the Lewis symbols for nitrogen and fluorine in Table 8.1, predict the formula of the stable binary compound (a compound composed of two elements) formed when nitrogen reacts
with fluorine and draw its Lewis structure.
nonmetals,
thehas
number
valence electrons
in a neutral atom is the same
he bonding electron pair, eachFor
chlorine
atom
eightofelectrons
(an octet)
SOLUTION
number.
Therefore,
one mightof
predict
that 7A elements, such as F, would
e shell, thus achieving the group
noble-gas
electron
configuration
argon.
Analyze
The Lewis
symbols for nitrogen and
fluorine
reveal that nitrogen has five valence
covalent
bond
achieve
an octet; 6A elements, such as O, would form two co
electrons
and to
fluorine
has seven.
uctures shown here for Hone
2 and Cl2 are called either Lewis structures or
We need tosuch
find a combination
of the two
elements
that results
in an4A
octetelements,
of electrons such as C,
bonds; 5A Plan
elements,
as N, would
form
three;
and
n-dot structures. In writing
Lewis
structures,
we
usually
show
each
shared
around each atom. Nitrogen requires three additional electrons to complete its octet, and flu Se
a diferena
na requires
habilidade
relativa
emofatrair
form
four. orine
These
predictions
are
borne
out inonemany
compounds,
as in, for examp
one. Sharing
a pair
electrons between
N atom and
one F atom will result
r as a line and any unshared
as uma
dots.
Written
way,
the
eltronselectron
grande
o pairs
suficiente,
ligao
inica
this
formada.
in an octet
of electrons
for
fluorine
but not
for nitrogen.
We
therefore
need to figure out a way
compounds
with
hydrogen
of
the
nonmetals
of
the
second
row of the periodic ta
to get two more electrons for the N atom.
ures for H2 and Cl2 are
Solve Nitrogen must share a pair of electrons with three fluorine atoms to complete its octet.
Ligaes covalentes
Eletronegatividade
Linus Pauling estabeleceu as eletronegatividades em uma escala

de 0,7 (Cs) a 4,0 (F).
Ligaes covalentes
Polaridade da ligao e eletronegatividade

Podemos usar a diferena na eletronegatividade entre
dois tomos para medir a polaridade da ligao entre

eles.
Se a diferena de eletronegatividade entre dois tomos for maior que 1,9

a ligao inica se for menor ou igual covalente polar. Se for igual ou menor que
0,5 covalente apolar.
Waals surface of a molecule since that represents

A map of electrostatic potential is prepared by carrying out
mately the
furthest extent
of a molecules electro
a quantum mechanical calculation that involves moving an
Ligaes
covalentes
and therefore its overall shape. The molecular mod
imaginary positive point charge at a fixed distance over a
box is for dimethyl ether. The MEP shows the conce
given electron density surface of a molecule. As this is done,
of negative charge where the unshared electron
the varying potential energy in the attraction between the
located on the oxygen atom.
electron cloud and the imaginary positive charge is plotted
It is important to note that when directly compa
in color-coded fashion. Red in the MEP indicates strong
MEP for one molecule to that of another, the color
attraction between the electron density surface at that locaused to represent the charge scale in each model
tion and the
probing positive
chargein
other words,
Lembrete:
mapa
de potencial
eletrosttico
the same. When we make direct comparisons betw
greater negative charge at that part of the surface. Blue
ecules, we will plot their MEPs on the same scale
regions in the map indicate weaker attraction between the
find that such comparisons are especially useful
surface and the positive charge probe. The overall distribthey allow us to compare the electron distributio
ution of charge is indicated by the trend from blue (most
molecule to that in another and predict how one m
positive or least negative) to green or yellow (neutral) to red
might interact with the electrons of another molec
(most negative). Most often we plot the MEP at the van der
Most positive
(Least negative)
Helpful Hin
Electron density surfac

electrostatic potential
Most negative
Dimethyl ether
mple of such a polar covalent bond is the one in hydrogen chloride. The chlorine
Ligaes covalentes
its greater electronegativity, pulls the bonding electrons closer to it. This makes
n atom somewhat electron deficient and gives it a partial positive charge (d!).
e atom
becomes
electron rich and59bears a partial negative charge (d"):
2.2 Polar
Covalentsomewhat
Bonds
Polaridade das ligaes

&!
&"
H C Cade
lC quo igualmente os eltrons em certa
uma medida
ligao
so has
compartilhados.
e hydrogen chloride
molecule
a partially positive end and a partially negaos dois
is a dipole, and it has a dipole moment.
ction of polarity of a polar bond can be symbolized by a vector quantity 199:.
end of the arrow is the positive end and the arrowhead is the negative end:
e is with a map of electrosta(positive
end) 199: (negative end)
ce that are more negative
than
operties and reactivity of molfunctional groups,

which we
are defined groups of atoms in
al properties) of the molecule.
electronegativity values and
medida que a diferena na eletronegatividade entre
and sulfur that form covalent
oms.)
tomos aumenta, aumenta tambm a polaridade.
ct a positively charged species

s negative (or are positive) are
her molecule. The spectrum of
most negative to least negative
example, we would indicate the direction of the dipole moment in the follow-
ow-electron-density surface of
is concentrated near the chloogen atom, as we predict based
ore, because this MEP is plotvan der Waals surface, Section
shape.
Figure 2.1 A calculated map

of electrostatic potential for
hydrogen chloride showing
regions of relatively more
negative charge in red and more
positive charge in blue. Negative
charge is clearly localized near
the chlorine, resulting in a strong
Qual das duas
dipole moment for the molecule.
H9Cl
199:
ole moment is a physical property that can be measured experimentally. It is

molculas
a mais
he product of the magnitude of the charge in
electrostatic
units eletronegativa?
(esu) and the
at separates them in centimeters (cm):
Dipole moment $ charge (in esu) # distance (in cm)
end)
(positive end) 199: (negative
Ligaes covalentes
electron deficient and gives it a partial positive ch

mple,
we
would
indicate
the
direction
of
the
dipole
omewhat
electron rich
bears a partial negative ch
Polaridade
dasand
ligaes
&!
&"
H C Ca lC
H 9 Cl
199:
Uma
vezphysical
que a molcula
do cloreto dethat
hidrognio
tembe
umameasur
moment
is
a
property
can
de molecule
hasparcialmente
a partially
positive
end and a part
extremidade
positiva
e uma extremidade
parcialmente negativa, ela um dipolo e tem um momento de
roduct
of
the
magnitude
of
the
charge
in
electros
dipolo.
has a dipole
moment.
Uma medida quantitativa da polaridade de uma ligao o seu
momentoin
de dipolo.
parates them
centimeters
(cm):
O momento
de dipolo
symbolized
uma propriedade fsicaby
que pode
ser medida quantit
f a polar bond
can
be
a
vector
experimentalmente.
Dipole moment $ charge (in esu) # distance (in
is the positive end and the arrowhead is the negative
%$e#d
ositive end) 199: (negative end)
"10
Ligaes covalentes

Da mesma forma que as ligaes individuais geralmente so
polares, as molculas como um todo tambm so.

Para uma molcula com mais de dois tomos, o momento de
dipolo depende tanto das polaridades das ligaes
individuais quanto da geometria da molcula.
Os dipolos de ligao e os momentos de dipolo so grandezas vetorias,
isto eles, possuem mdulo, direo e sentido.
O dipolo total de uma molcula poliatmica a soma total de seus dipolos
de ligao.
Figure 2.2 Charge distribution

in carbon tetrachloride. The
molecule has no net dipole
moment.
The chloromethane
Cl
2.3 Polar and N
Ligaes covalentes
molecule (CH3Cl) has a net dipole moment of

and( 1hydrogen
have electronegativities (Table 1.2) that are nearly the s
9: ) to repThis result can be illustrated in a slightly different way: If we use arrows
resent the direction of polarity of each bond, we get the arrangement of bond
moments
shown
of three
C9
H bonds to the net dipole is negligible. The electronegativi
in Fig. 2.3. Since the bond moments are vectors of equal magnitude arranged
tetrahedrally,
carbon
and chlorine is large, however, and the highly polar C 9 Cl bo
their effects cancel. Their vector sum is zero. The molecule has no net dipole
moment.
of the dipole moment of CH3Cl (Fig. 2.4).

Cl
Cl
C
Cl
Cl
Cl
"=0D
Figure 2.3 A tetrahedral

orientation of equal bond
moments causes their effectsH
to cancel.
! = 1.87 D
(a)
(b)
Figure 2.4 (a)

moment of chl
arises mainly f
polar carbonc
(b) A map of e
potential illust
of chlorometh
Solved Problem 2.3
Although molecules of CO2 have polar bonds (oxygen is mo

(Table 2.1) has no dipole moment. What can you conclude abou
STRATEGY AND ANSWER For a CO2 molecule to have a z
moments of the two carbonoxygen bonds must cancel each othe

ecules of carbon dioxide are linear.
Boron trifluoride (BF3) has no dipole moment (m ! 0 D). Explain

confirms the geometry of BF3 predicted by VSEPR theory.
Ligaes covalentes
Exercitando
Ligaes covalente
How does Lewis theory explain the bonds in H2 and F2?
Sharing of two electrons between the two atoms.

Bond Dissociation Energy
Bond Length
Overlap Of
H2
436.4 kJ/mole
74 pm
2 1s
F2
150.6 kJ/mole
142 pm
2 2p
Valence bond theory bonds are formed by sharing

of e- from overlapping atomic orbitals.
Ligaes covalente
Ligao Covalente
Atualmente, so usadas duas teorias, que tm base na
mecnica quntica, para descrever a formao da ligao

covalente.
A teoria da ligao de valncia (TLV).
A teoria dos orbitais moleculares (TOM).
Cada uma delas tem dado sua contribuio para a nossa
compreenso de muitas propriedades moleculares

observadas.
possveis, isto no realmente muito importante. As molculas podem girar

sobre seus prprios eixos, os eltrons podem ter spins e fases alterados, de
modo que os requisitos para que ocorra a reao podem sempre ser
preenchidos. Consideraes sobre essas questes de fase poderiam no mximo
Ligaes covalente
explicar alguma alterao de velocidade. No entanto, quando os tomos que
vo reagir fazem parte da mesma molcula, a coisa pode mudar de figura: as
fases dos orbitais que vo interagir podem ser determinadas por um conjunto
de orbitais que existem na mesma molcula, e a rotao restrita pode no
permitir que os orbitais que vo interagir mudem muito de posio; nessas
circunstncias as fases podem explicar a diferena entre uma substncia que
reage muito bem e outra substncia, que pode nos parecer muito semelhante,
mas que no reage de modo algum. Outro caso quando duas molculas
reagem ligando-se simultaneamente por dois pontos: as fases dos vrios
orbitais podem favorecer ou no a ocorrncia da reao.
Teoria da ligao de valncia

Essa teoria foi desenvolvida por Linus Pauling.
As ligaes se formam quando um orbital atmico de um

Hibridizao7
tomo se superpem ao orbitalA atmico

defoioutro
tomo.
teoria da hibridizao
inicialmente
proposta por Linus Pauling
para
explicar a geometria dos compostos orgnicos. Acabou se tornando uma teoria
extremamente valiosa e importante porque explica simultaneamente a geometria e a
valncia (que, por outras teorias, seria considerada
anmala) no s do carbono e seus compostos, mas
tambm dos outros elementos.
Quando pensamos em como os
tomos que constituem uma molcula esto dispostos
no espao uns em relao aos outros (o que estivemos
chamando acima de geometria da molcula),
percebemos que:
1. Se tivermos apenas dois tomos,
consideramos apenas a distncia entre eles
(distncia entre os centros dos ncleos).
2. Se tivermos trs tomos, temos que
considerar ainda o ngulo formado pelos
eixos das duas ligaes (os eixos so as
retas que passam pelo centro dos dois
ncleos);
Tambm chamada hibridao; h um certo desacordo entre autores sobre qual seria a forma mais
Ligaes covalente
TLV
Formao da molcula de hidrognio (H2)
DDDDDD
DDDDDD
DDDDDD
DDDDDD
DDDDDD
Ligaes covalente
Formao da molcula de hidrognio (H2)
medida que dois tomos se aproximam, seus orbitais atmicos se superpem.

medida que a superposio aumenta, a energia de interao diminui.
A uma determinada distncia, a energia mnima alcanada.
A energia mnima corresponde distncia de ligao (ou comprimento de ligao).
Quando os dois tomos ficam mais prximos, seus ncleos comeam a se repelir e a
energia aumenta.
Ligaes covalente
HIBRIDIZAO
Quando aplicamos a TLV s molculas poliatmicas,
devemos explicar tanto as ligaes por pares de eltrons

quanto as geometrias observadas para as molculas.
Para descrever a ligao no metano e em outras
molculas, Linus Pauling props a teoria da hibridizao
dos orbitais.
Ligaes covalente
Ligao no metano
The BasicsBonding and Molecular Structure
Como approach
explicar
a formao
de ofquatro
ligaes
se o
ore than a mathematical
that involves
the combining
individual
wave
carbono
possui
apenasfordois
desemparelhados?
or s and p orbitals
to obtain
wave functions
new eltrons
orbitals. The
new orbitals
rying proportions, the properties of the original orbitals taken separately. These
ls are called hybrid atomic orbitals.
No estado fundamental, a configurao do tomo de carbono :
ing to quantum mechanics, the electronic configuration of a carbon atom in its
rgy statecalled the ground stateis that given here:
C u u n
n
1s 2s 2px 2py 2pz
Ground state of a carbon atom
e electrons of a carbon atom (those used in bonding) are those of the outer level,
2s and 2p electrons.
The Structure of Methane
Com essa distribuio eletrnica, o carbono no capaz de se ligar a quatro

omic orbitalstomos
that account
for the mas
structure
of dois.
methane can be derived from
de hidrognio,
apenas
econd-shell s and p orbitals as follows (Fig. 1.12):
e functions for the 2s, 2px, 2py, and 2pz orbitals of ground state carbon are
ed to form four new and equivalent 2sp3 hybrid orbitals.
Ligaes covalente
Ligao no metano
Se o carbono usou um orbital s e trs orbitais p para formar as quatro ligaes, a

ligao formada com o orbital s seria diferente das trs ligaes formadas com o
orbitais p.
Ligaes covalente
Ligao no metano
Como o carbono pode formar quatro ligaes idnticas,
usando um orbital s e trs p?

A resposta que o carbono usa orbitais hbridos.
So orbitais atmicos obtidos quando dois ou mais orbitais no
equivalentes do mesmo tomo se combimam para a formao de

ligaes covalentes.
can be explained by the similar electronegativities of carbon and hydrogen, which

cause carbon and hydrogen to share their bonding electrons relatively equally.
Methane is a nonpolar molecule.
Ligaes
You may be surprised to learn that carbon forms four covalent bonds since you
know that carbon has only two unpaired electrons in its ground-state electronic configuration (Table 1.2). But if carbon were to form only two covalent bonds, it would
not complete its octet. Now we need to come up with an explanation that accounts for
carbons forming four covalent bonds.
If one of the electrons in the 2s orbital were promoted into the empty 2p atomic orbital, the new electronic configuration would have four unpaired electrons; thus, four
covalent bonds could be formed. Lets now see whether this is feasible energetically.
covalente
Ligao no metano
BRUI01-001_059r4 20-03-2003 2:58 PM Page 27
promotion
s
after promotion
before promotion
Because a p orbital is higher in energy than an s orbital, promotion of an electron

Section
1.7 Bonding
from an s orbital to a p orbital requires energy. The amount
of energy
requiredinisMethane and Ethane: Single Bonds
96 kcal>mol. The formation of four C H bonds releases 420 kcal>mol of energy bewiththeone
s orbital
to formenergy
the hybrid
Each
25% s character
sp 3 orbital
H bond
kcal>mol.
cause
bond
dissociation
of a orbitals.)
single C
is 105has
If the
3
and 75%
character.
The carbon
four spcould
orbitals
degeneratethey
have the
same
energy.
electron
werep not
promoted,
formare
only
two covalent bonds,
which
would
release only 210 kcal>mol. So, by spending 96 kcal>mol (or 402 kJ> mol) to promote
an electron, an extra 210 kcal>mol (or 879 kJ> mol) is released. In other words, promohybridization
p
p
p
tion is energetically advantageous (Figure 1.9).
sp 3
sp 3
sp 3
sp 3
s
Figure 1.9 N
hybrid orbitals
4 orbitals
are
hybridized
As a result of
electron
promotion,
Potential energy
carbon forms four covalent bonds

and releases
kcal> mol
Like a420
p orbital,
anofsp 3 orbital has two lobes. The lobes differ
in size, however, be420 kcal/mol
energy. Without promotion, carbon
promotion
cause the s orbital adds to one lobe of the p orbital
and subtracts from the other lobe of
would form two covalent bonds
3
96
kcal/mol
p orbital
(Figure
The stability of an sp orbital reflects its composition; it is
andthe
release
210 kcal
of energy.
> mol 1.10).
4 covalent
moreitstable
than
p orbital,
1.11). The larger
Because
requires
96 akcal
> mol to but not as stable as an s orbital (Figure
bonds
3
promote
an
electron,
the
overall
lobe of the sp orbital is used in covalent bond formation.
energy advantage of promotion is
114 kcal>mol.
BRUI01-001_059r4 20-03-2003 2:58 PM Page 27
Section 1.7
Bonding in Methane and Ethane: Single Bonds
Ligaes covalente
with one s orbital to form the hybrid orbitals.) Each sp 3 orbital has 25% s character
and 75% p character. The four sp 3 orbitals are degeneratethey have the same energy.
Ligao no metano
p
hybridization
Section 1.7
3
27
27
sp orbitals.)
sp Each sp
sp has 25% s character
with one s orbital to form the hybrid
sp 3 orbital
3
and 75% p character. The four sp orbitals are degeneratethey have the same energy.
hybrid orbitals
4 orbitals are hybridized
sp
sp
sp
O nmero3 de
orbitais hbridossp em
um
tomo igual ao
s
hybridization
Like a p orbital, an sp orbital has two lobes. The lobes differ in size, however,
behybrid orbitals
cause the s orbital adds to one lobe
of
the
p
orbital
and
subtracts
from
the
other
lobe
of
3
the p orbital (Figure 1.10). The stability of an3 sp orbital reflects its composition; it is
p orbital,
an sp as
orbital
two lobes.
The lobes
differ
in size,
however, bemore
stable than a p orbital,Like
buta not
as stable
an shas
orbital
(Figure
1.11).
The
larger
cause the s orbital adds to one lobe of the p orbital and subtracts from the other lobe of
3
lobe of the sp orbital is used
in covalent
formation.
the p orbital
(Figure bond
1.10). The
stability of an sp 3 orbital reflects its composition; it is
nmero de orbitais atmicos que se misturaram.

Os orbitais hbridos tem formas diferentes dos orbitais
stable than a p orbital, but not as stable as an s orbital (Figure 1.11). The larger
atmicos. more
lobe of the sp orbital is used in covalent bond formation.
3
the s orbital adds to

the lobe of the p orbital
> Figure 1.10
The s orbital adds to one lobe of
> Figure
the s orbital addsthe
to p orbital
and1.10
subtracts from the
other lobe
the p and
orbital.
theof
p orbital
subtracts from the
s orbital
other lobe of the p orbital.
s orbital
p orbital
p orbital
the s orbital
subtracts from
the s orbital subtracts
from
> Figure 1.11
s orbital and three p orbitals

> FigureAn1.11
3
hybridization
hybridization
p
p
sp 3
sp 3
p
s
sp 3
hybridize to form four sp orbitals.

An s orbital
and three p orbitals
An sp3 orbital is more
hybridizestable
to form
sp3 orbitals.
than four
a p orbital,
but not as
3
An sp orbital
is an
more
stable as
s orbital.
stable than a p orbital, but not as
stable
as an s orbital.
sp 3
sp 3
sp 3
sp 3
sp 3
The four sp 3 orbitals arrange themselves in space in a way that allows them to get
59r4 20-03-2003 2:58 PM Page 27
Ligaes covalente
Section 1.7
ith one s orbital to form the hybrid orbitals.) Each sp 3 orbital has 25% s character
nd 75% p character. The four sp 3 orbitals are degeneratethey have the same energy.
Ligao no metano
solom_c01_001-052hr1.qxd
27
hybridization
sp 3
sp 3
sp 3
14-10-2009
14:20
Page 27
sp 3
hybrid orbitals
Like a p orbital, an sp 3 orbital has two lobes. The lobes differ in size, however, beause the s orbital adds to one lobe of the p orbital and subtracts from the other lobe of
e p orbital (Figure 1.10). The stability of an sp 3 orbital reflects its composition; it is
ore stable than a p orbital, but not as stable as an s orbital (Figure 1.11). The larger
be of the sp 3 orbital is used in covalent bond formation.
the s orbital adds to

> Figure 1.10

the p orbital and subtracts from the
other lobe of the p orbital.
1.12 The Structure of Methane and Ethane: sp3 Hybridization
s orbital
p orbital
the s orbital subtracts from

> Figure 1.11
An s orbital and three p orbitals

hybridize to form four sp3 orbitals.
An sp3 orbital is more
stable than a p orbital, but not as
stable as an s orbital.
hybridization
p
sp 3
sp 3
sp 3
sp 3
109.5
The four sp orbitals arrange themselves in space in a way that allows them to get
s far away from each other as possible (Figure 1.12a). This occurs because electrons
pel each other and getting as far from each other as possible minimizes the repulsion
Section 1.6). When four orbitals spread themselves into space as far from each other
s possible, they point toward the corners of a regular tetrahedron (a pyramid with four
b.
> Figure 1.12
C
H
(a) The four sp3 orbitals are

directed toward the corners of a
tetrahedron, causing each bond
angle to be 109.5.
(b) An orbital picture of methane,
showing the overlap of each sp3
orbital of carbon with the s
orbital of a hydrogen. (For clarity,
the smaller lobes of the sp3
orbitals are not shown.)
C
H
H
H
Methane, CH4
Figure 1.13 The hypoth

methane from an sp3-hyb
atom and four hydrogen
hybridization we combin
electrons. The electrons
in the hybrid orbitals as n
formation, but always in
Pauli principle of no mor
(with opposite spin) in ea
illustration we have place
each of the hybrid carbo
we have shown only the
orbital of each C 9 H bon
the orbitals that contain
lowest energy state of th
If, in our imagination, we visualize the hypothetical formation of methane from an sp3hybridized carbon atom and four hydrogen atoms, the process might be like that shown in
Ligaes covalente
Ligao no metano
Resumo:
Os orbitais hbridos sp3 so formados a partir de um orbital s e trs
orbitais p.
Cada lbulo aponta em direo ao vrtice de um tetraedro.
O ngulo entre os grandes lbulos de 109,5!.
Todas as molculas com arranjos tetradricos so hibridizadas sp3.
It is important to understand
what molecules
lookcan
like inbe
three
dimensions.
As you
study
three-dimensional representations
of molecules
that
found
in the
molecule
gallery
each chapter, make sure to visit the Web site www.prenhall.com/bruice and look at the
that accompanies the chapter.
three-dimensional representations of molecules that can be found in the molecule gallery
Ligaes covalente
Bonding in Ethane
Bonding in Ethane
The two carbon atoms in ethane are tetrahedral. Each carbon uses four sp 3 orbitals to
Ligao no Etano
formin
four
covalent bonds:
The two carbon atoms
ethane
are tetrahedral. Each carbon uses four sp 3 orbitals to
H H
form four covalent bonds:
C
H HH
H
ethane
One sp 3 orbital of one carbon overlaps an sp 3 orbital of the other carbon to form
the C C bond. Each of the remaining three sp 3 orbitals of each carbon overlaps
H a C H bond. Thus, the C C bond is
H form
the s orbital of a hydrogen to
formed by sp 3sp 3 overlap, ethane
and each C H bond is formed by sp 3s overlap
(Figure 1.13). Each of the bond angles in ethane is nearly the tetrahedral bond angle
of 109.5, and the length of the C C bond is 1.54 . Ethane, like methane, is a
3
nonpolar molecule.
One sp 3 orbital of one carbon overlaps an sp orbital of the other carbon to form
the C C bond. Each of the remaining three sp 3 orbitals of each carbon overlaps
H
H 109.6
of
the s orbital
a hydrogen
to form a C H bond. Thus, the C C bond is
1.10 A
3
3
3
H
sp
formed by sp
C
Coverlap, and each C H bond is formed by sp s overlap
H
(Figure 1.13). Each
of
Hthe bond angles in ethane is nearly the tetrahedral bond angle
H 1.54 A
model
electrostatic
potential
formula
model
C bondspace-filling
. Ethane,
of 109.5, andperspective
the
length
of ball-and-stick
theofCethane
isof1.54
like
methane, is a
ethane
map for ethane
of ethane
nonpolar molecule.
H
109.6 H
C
H
C
H
H
H
C
three-dimensional representations of molecules that can be found in the molecule gallery

Ligaes covalente
Bonding in Ethane
sp 3 orbitals to
The two carbon atoms in ethane are tetrahedral. Each carbon uses four
1.12 The Structure of Methane and Ethane: sp3 Hybridization
form four covalent bonds:
Ligao no Etano
H H
H
H H
29
ethane
One sp 3 orbital of one carbon overlaps an sp 3 orbital of the other carbon to form
sp 3 orbitals of each carbon overlaps
the C C bond.
Each of the remaining three
sp 3 Carbon
sp 3 Carbon
the s orbital of a hydrogen to form a C H bond. Thus, the C C bond is
formed by sp 3sp 3 overlap, and each C H bond is formed by sp 3s overlap
(Figure 1.13). Each of the bond angles in ethane is nearly the tetrahedral bond angle
of 109.5, and the length of the C C bond is 1.54 . Ethane, like methane, is a
nonpolar molecule.
H
H 109.6 H
1.10 A
H
Sigma bonds
Figure 1.18 The hypothetical formation of

the bonding molecular orbitals of ethane
from two sp3-hybridized carbon atoms and
six hydrogen atoms. All of the bonds are
sigma bonds. (Antibonding sigma molecular
electrostatic potential
orbitalscalled s* orbitalsare formed in
map for ethane
each instance as well, but for simplicity
these are not shown.)
A sigma
bond
H
H 1.54 A
perspective formula
of ethane
ball-and-stick model
of ethane H
space-filling model
H
of ethane
H
H
Figure 1.13
(a)
(b)
CH
H
H
(c)
3
H
H
Figure 1.19
H (a) In this structure of ethane, based
on quantum mechanical calculations, the inner solid
surface represents
H a region of high electron density.
High electron density is found in each bonding
C The outer mesh surface represents
region.
approximately the furthest extent of overall electron
density for the molecule. (b) A ball-and-stick model
of ethane,Hlike the kind you might build with a
molecular model kit. (c) A structural formula for
ethane as you would draw it using lines, wedges,
and dashed wedges to show in three dimensions its
tetrahedral geometry at each carbon.
Ligaes covalente
Ligao no eteno
Ligaes covalente
Ligao no eteno
Ligaes covalente
Ligao no eteno
Ligaes covalente
Ligao no eteno
Ligaes covalente
Ligao no eteno
Ligaes covalente
Ligao no eteno
Importante:
Os orbitais hbridos sp2 so formados com um orbital s e dois
orbitais p.
(Conseqentemente, resta um orbital p nohibridizado.)
Todas as molculas com arranjos trigonais planos tm orbitais
sp2 no tomo central.
uma ligao ! e uma ligao !;
ambos os tomos de C esto hibridizados sp2;
ambos os tomos de C possuem arranjos e geometrias
moleculares trigonais planos.
Ligaes covalente
Ligao no etino
Ligaes covalente
Ligao sigma (): Licaes covalentes formadas pela
superposio dos orbitais pelas suas extremidades, com a

densidade eletrnica concentrada entre os ncleos
envolvidos na ligao.
SECTION 9.4
Covalent Bonding and Orbital Overlap
345
Because the octahedral molecular geometry is symmetrical, the bond dipoles cancel, and the
molecule is nonpolar, meaning that m = 0.
PRACTICE EXERCISE
Determine whether the following molecules are polar or nonpolar: (a) NF3, (b) BCl3.
Answers: (a) polar because polar bonds are arranged in a trigonal-pyramidal geometry,
(b) nonpolar because polar bonds are arranged in a trigonal-planar geometry
9.4 COVALENT BONDING AND

ORBITAL OVERLAP
The VSEPR model provides a simple means for predicting molecular geometries but
does not explain why bonds exist between atoms. In developing theories of covalent
bonding, chemists have approached the problem from another direction, using quantum mechanics. How can we use atomic orbitals to explain bonding and to account for
molecular geometries? The marriage of Lewiss notion of electron-pair bonds and the
idea of atomic orbitals leads to a model of chemical bonding, called valence-bond
theory, in which bonding electron pairs are concentrated in the regions between atoms
and nonbonding electron pairs lie in directed regions of space. By extending this approach to include the ways in which atomic orbitals can mix with one another, we
obtain an explanatory picture that corresponds to the VSEPR model.
In Lewis theory, covalent bonding occurs when atoms share electrons because the
sharing concentrates electron density between the nuclei. In valence-bond theory, we visualize the buildup of electron density between two nuclei as occurring when a valence
atomic orbital of one atom shares space, or overlaps, with a valence atomic orbital of another atom. The overlap of orbitals allows two electrons of opposite spin to share the
space between the nuclei, forming a covalent bond.
The coming together of two H atoms to form H2 is depicted in ! FIGURE 9.13.
Each atom has a single electron in a 1s orbital. As the orbitals overlap, electron density is
concentrated between the nuclei. Because the electrons in the overlap region are simultaneously attracted to both nuclei, they hold the atoms together, forming a covalent
bond.
The idea of orbital overlap producing a covalent bond applies equally well to other
molecules. In HCl, for example, chlorine has the electron configuration [Ne]3s23p5. All
the valence orbitals of chlorine are full except one 3p orbital, which contains a single
1s
1s
H2
1s
3p
Cl
3p
3p
Cl
Cl
" FIGURE 9.13 Covalent bonds in H2,

HCl, and Cl2 result from overlap of atomic
orbitals.
Ligaes covalente
Ligaes pi (): ligao covalente formada pela
superposio lateral dos orbitais, com densidade eletrnica

concentrada acima e abaixo do plano que contm os
ncleos dos tomos envolvidos em uma ligao pi.
Ligaes covalente
Ligao no etino
Ligao no etino
Ligaes covalente
o arranjo de cada C linear;

conseqentemente, os tomos de C so hibridizados sp;
os orbitais hbridos sp formam as ligaes ! C-C e C-H;
h dois orbitais p no-hibridizados;
ambos os orbitais p no-hibridizados formam as duas ligaes
!;
uma ligao ! est acima e abaixo do plano dos ncleos;
uma ligao ! est frente e atrs do plano dos ncleos.
Ligaes covalente
Ligaes mltiplas
Ligaes !: a densidade eletrnica encontra-se no eixo entre

os ncleos.
Todas as ligaes simples so ligaes !.
Ligaes !: a densidade eletrnica encontra-se acima e
abaixo do plano dos ncleos.
Uma ligao dupla consiste de uma ligao ! e de uma
ligao !.
Uma ligao tripla tem uma ligao ! e duas ligaes !.
Normalmente, os orbitais p envolvidos nas ligaes ! vm
de orbitais no-hibridizados.
Ligaes covalente
Ligao na gua
Ligaes covalente
Ligao na amnia
Ligaes covalente
O efeito dos eltrons no-ligantes e ligaes
mltiplas nos ngulos de ligao

H
H C H
H
109.5O
H N H
H
107O
H
H
104.5O
Como os eltrons em uma ligao so atrados por dois ncleos, eles no se

repelem tanto quanto os pares solitrios. Conseqentemente, os ngulos de
ligao diminuem quando o nmero de pares de eltrons no-ligantes aumenta.
Ligaes covalente
O efeito dos eltrons no-ligantes e ligaes

mltiplas nos ngulos de ligao
Da mesma forma, os eltrons nas ligaes mltiplas se
repelem mais do que os eltrons nas ligaes simples.
Cl
111.4o
Cl
C O
124.3o
hybridized carbon (33.3% s), which in turn is shorter and stronger than a C H bond
formed by an sp 3 hybridized carbon (25% s).
The bond angle also depends on the orbital used by carbon to form the bond. The
greater the amount of s character in the orbital, the larger is the bond angle. For example, sp hybridized carbons have bond angles of 180, sp 2 hybridized carbons have
bond angles of 120, and sp 3 hybridized carbons have bond angles of 109.5.
Table 1.7
The more s character, the shorter and

stronger is the bond.
Ligaes covalente
The more s character, the larger is the
bond angle.
Comparison of the Bond Angles and the Lengths and Strengths of the CarbonCarbon
and CarbonHydrogen Bonds in Ethane, Ethene, and Ethyne
Molecule
Length of
Strength of
C C bond
C C bond
()
(kcal>mol) (kJ>mol)
Length of
Strength of
C H bond
C H bond
()
(kcal>mol)
(kJ>mol)
Hybridization
of carbon
Bond
angles
sp 3
109.5
1.54
90
377
1.10
101
423
sp 2
120
1.33
174
720
1.08
111
466
sp
180
1.20
231
967
1.06
131
548
H H
H
H H
ethane
H
C
H
ethene
ethyne
sp 5% de s
sp2 33% de s
sp3 25%
Ethers generally have higher boiling points than alkanes of comparable molecular
weight because both van der Waals forces and dipoledipole interactions must be
overcome for an ether to boil (Table 2.5).
More extensive tables of physical properties can be found in Appendix I.
Foras intermoleculares
O
cyclopentane
bp = 49.3 C
tetrahydrofuran
bp = 65 C
As the table shows, alcohols have much higher boiling points than alkanes or ethers
of comparable molecular weight because, in addition to van der Waals forces and the
dipoledipole interactions of the C O bond, alcohols can form hydrogen bonds. A
hydrogen bond is a special kind of dipoledipole interaction that occurs between a hydrogen that is bonded to an oxygen, a nitrogen, or a fluorine and the lone-pair electrons of an oxygen, nitrogen, or fluorine in another molecule.
The length of the covalent bond between oxygen and hydrogen is 0.96 . The hydrogen bond between an oxygen of one molecule and a hydrogen of another molecule
is almost twice as long (1.691.79 ), which means that a hydrogen bond is not as
strong as an O H covalent bond. A hydrogen bond, however, is stronger than other
Esto diretamente relacionadas a propriedades como

ponto de fuso, ponto de ebulio e a energia necessria
para converter um slido em m liquido ou um lquido em
vapor.
Table 2.5
Comparative Boiling Points (C)
Alkanes
Ethers
Alcohols
Amines
CH 3CH 2CH 3
CH 3OCH 3
CH 3CH 2OH
CH 3CH 2NH 2
!42.1
!23.7
78
16.6
CH 3CH 2CH 2CH 3
CH 3OCH 2CH 3
CH 3CH 2CH 2OH
CH 3CH 2CH 2NH 2
! 0.5
10.8
97.4
47.8
CH 3CH 2CH 2CH 2CH 3
CH 3CH 2OCH 2CH 3
CH 3CH 2CH 2CH 2OH
CH 3CH 2CH 2CH 2NH 2
36.1
34.5
117.3
77.8
Ligao intramolecular
Existem quatro tipos de foras atrativas entre molculas:
Foras dipolo-dipolo
Disperso de London
Ligaes de hidrognio
on-dipolo
INTERAO ON-DIPOLO
A mais forte de todas as foras intermoleculares
H
H
+ H
H
H +
O
H
Na+
O
H
Cl
H
H
H
O
H
2.13B Intermolecular Forces (van der Waals Forces)
Introduction to Organic
Laboratory Techniques: A
The forces that act between molecules are not as strong as those between
ions, but
they Microscale Approach (with
Foras
intermoleculares
account for the fact that even completely nonpolar molecules can exist in liquid and solid Periodic Table), 3E. 199
states. These intermolecular forces, collectively called van der Waals forces, are all elec- Brooks/Cole, a part of Ce
Learning, Inc. Reproduced
trical in nature. We will focus our attention on three types:
permission. www.cengage
permissions.
INTERAO DIPOLO-DIPOLO
1. Dipoledipole forces
2. Hydrogen bonds
3. Dispersion forces
DipoleDipole Forces Most organic molecules are not fully ionic but have instead a
permanent dipole
distribution of
the bonding
ou
+ moment
resulting
+ from a nonuniform
+ electrons (Section 2.3). Acetone and acetaldehyde are examples of molecules with permanent
dipoles because the carbonyl group that they contain is highly polarized. In these compara
molculas
polares In the liquid
pounds, the attractiveOrientaes
forces between possveis
molecules are
much
easier to visualize.
or solid state, dipoledipole attractions cause the molecules to orient themselves so that
the positive end of one molecule is directed toward the negative end of another (Fig. 2.7).
H3C
+ C
H3C
H3C
+ C
H3C
H3C
+ C
H3C
Figure 2.7 Electrostatic potential

models for acetone molecules that show
how acetone molecules might align
according to attractions of their partially
positive regions and partially negative
regions (dipoledipole interactions).
Hydrogen Bonds
!
Very strong dipoledipole attractions occur between hydrogen atoms bonded to

small, strongly electronegative atoms (O, N, or F) and nonbonding electron pairs
on other such electronegative atoms. This type of intermolecular force is called a
INTERAO DIPOLO-DIPOLO
Mais fracas do que as foras on-dipolo.
Se duas molculas tm aproximadamente a mesma
massa e o mesmo tamanho, as foras dipolo-dipolo

aumentam com o aumento da polaridade.
INTERAO DIPOLO INSTANTNEO-DIPOLO

INDUZIDO
Foras de disperso de London
So causadas por oscilaes momentneas de carga do eltron em
tomos e, portanto, esto presentes entre todas as partculas (tomos,
ons e molculas).
choque
+
Dipolo instatneo
Interao dipolo instantneodipolo induzido
Ethers generally have higher boiling points than alkanes of comparable molecular
weight because both van der Waals forces and dipoledipole interactions must be
overcome for an ether to boil (Table 2.5).
More extensive tables of physical properties can be found in Appendix I.
cyclopentane
bp = 49.3 C
tetrahydrofuran
bp = 65 C
INTERAO DIPOLO INSTANTNEO-DIPOLO

INDUZIDO
As the table shows, alcohols have much higher boiling points than alkanes or ethers
of comparable molecular weight because, in addition to van der Waals forces and the
dipoledipole interactions of the C O bond, alcohols can form hydrogen bonds. A
hydrogen bond is a special kind of dipoledipole interaction that occurs between a hydrogen that is bonded to an oxygen, a nitrogen, or a fluorine and the lone-pair electrons of an oxygen, nitrogen, or fluorine in another molecule.
The length of the covalent bond between oxygen and hydrogen is 0.96 . The hydrogen bond between an oxygen of one molecule and a hydrogen of another molecule
is almost twice
long (1.691.79
), a
which
means
a hydrogen
bond
is not
as
asQuanto
maior
rea
de that
contato
maior
a interao.
strong as an O H covalent bond. A hydrogen bond, however, is stronger than other
Table 2.5
Comparative Boiling Points (C)
Alkanes
Ethers
Alcohols
Amines
CH 3CH 2CH 3
CH 3OCH 3
CH 3CH 2OH
CH 3CH 2NH 2
!42.1
!23.7
78
16.6
CH 3CH 2CH 2CH 3
CH 3OCH 2CH 3
CH 3CH 2CH 2OH
CH 3CH 2CH 2NH 2
! 0.5
10.8
97.4
47.8
CH 3CH 2CH 2CH 2CH 3
CH 3CH 2OCH 2CH 3
CH 3CH 2CH 2CH 2OH
CH 3CH 2CH 2CH 2NH 2
36.1
34.5
117.3
77.8
TEMPERATURA DE EBULIO DE ALCANOS DE MESMA MASSA

MOLECULAR
H3C CH2 CH2 CH2 CH3
Pentano
Te= 36 C
H3C CH2 CH2 CH3

CH3
2-metilbutano
Te= 28 C
CH3
H3C C CH3
CH3
2,2-dimetipropano
Te= 9,5 C
LIGAO DE HIDROGNIO
Caso especial de foras dipolo-dipolo que ocorre entre um
hidrognio ligado a um oxignio, um nitrognio ou um flor e um

par de eltrons livres de um oxignio, um nitrognio ou um flor de
outra molcula..
- INTERMOLECULAR
H
O
....... H
H
O
H N H .......
H
- INTRAMOLECULAR
O
....
O
....
O
H
O
H
N H
H
H3C
O
....... H
H
O
H3C
H
O
H
O
No ocorre formao de ligao

de hidrognio intramolecular
bonding, water would have a boiling point near !80C and would not exist as a liquid unless
One of thewere
most important
consequences
of hydrogen
bonding
is thatthe
it causes
be
the temperature
lower than
that temperature.
Had
this been
case, water
it is tohighly
a liquid rather than a gas at 25C. Calculations indicate that in the absence of hydrogen
unlikely
that life,
as we
know
it,a boiling
could have
developed
on the
planet
Earth.
Water molecules associated
by
bonding,
water
would
have
point
near
!80C
and
would
not
exist
as a liquid unless
Foras
intermoleculares
attraction of opposite partial Hydrogen bonds hold the base pairs of double-stranded DNA together (see Section 25.4).
the temperature were lower than that temperature. Had this been the case, it is highly
charges.
Thymineunlikely
hydrogen
bonds
with
adenine.
Cytosine
hydrogen
bonds
with
guanine.
that life,
as we
know
it, could
have developed
on the
planet
Earth.
Hydrogen
bonding
accounts
fact
that ethyl alcohol
a much
higher 25.4).
boiling
Hydrogen
bonds
hold the for
basethe
pairs
of double-stranded
DNAhas
together
(see Section
Thymine hydrogen
bonds with
Cytosine
with
guanine. have the
point ("78.5C)
than dimethyl
etheradenine.
(!24.9C)
evenhydrogen
though bonds
the two
compounds
attraction of opposite partial

charges.
Hydrogen bonding accounts

for IDROGNIO
the fact that ethyl alcohol has a much higher boiling
LIGAO
D
E
H
H even though the two compounds have the
point ("78.5C) than dimethyl ether (!24.9C)
H
H3C
O
H3C
N
DNA backbone
HNN
N
N
Thymine
DNANbackbone
DNA backbone
Thymine
N
H
NH
Adenine
Adenine
H
N
N
O
H N
N
DNA backbone
DNA backbone N
O
H N
DNA backbone
H
H
Cytosine
Guanine
Cytosine
N
N DNA backbone
DNA backbone
Guanine
same molecular weight. Molecules of ethyl alcohol, because they have a hydrogen atom
same molecular weight. Molecules of ethyl alcohol, because they have a hydrogen atom
covalently
bondedbonded
to an to
oxygen
atom,
cancan
form
strong
toeach
eachother.
other.
covalently
an oxygen
atom,
form
stronghydrogen
hydrogen bonds
bonds to
d" d"
CH3CH
CH
2 3CH2
d!
d!
d"
O
H
d" d!
H
H
d!
HO O
3
CH2CH
CH2CH
3
The
red
The
reddots
dotsrepresent
represent aa
hydrogen
bond.
hydrogen bond. Strong
Strong
hydrogenbonding
bonding is
hydrogen
is
limitedto
tomolecules
molecules
limited
havinga ahydrogen
hydrogen atom
having
atom
attached to an O, N, or
attached to an O, N, or
F atom.
F atom.
Molecules of dimethyl ether, because they lack a hydrogen atom attached to a strongly elec-
Os pontos
de
ebulio
olack
peso
molecular,
porIn causa
do the
Molecules
of dimethyl
ether,
theyhydrogen
a hydrogen
attached
to a strongly
electronegative
atom,aumenta
cannotbecause
form com
strong
bonds
to atom
each other.
dimethyl
ether
tronegative
atom, cannot
form
strong
hydrogen bonds
to each other. In dimethyl ether the
aumento
nas
foras
deforces
Van
Waals.
intermolecular
areder
weaker
dipoledipole
interactions.
intermolecular forces are weaker dipoledipole interactions.
Review Problem 2.25
Review Problem 2.25
The compounds in each part below have the same (or similar) molecular weights. Which compound in each
partpart
would
you expect
to have
boiling
point? Explain
your
answers.
The compounds
in each
below
have the
samethe
(orhigher
similar)
molecular
weights.
Which
com-
pound in(a)each part would

boiling
Explain yourCH
answers.
, higher(b)
(CH3)point?
OHyouorexpect toOhave the
3,
3N or
(a)
(c)
or
OH OH
or
HO
O
OH . (b) (CH3)3N
or
N
H
CH3 ,
TEMPERATURA DE EBULIO VS FORAS

INTERMOLECULARES
Efeitos eletrnicos
Efeito sobre a estrutura ou reatividade que atribudo
alterao da distribuio dos eltrons causada por um

substituinte em uma molcula.
1) Efeito indutivo:
Chama-se efeito indutivo o efeito produzido por um tomo ou grupo de
tomos, pertencente a uma mollcula, que resulta de sua capacidade

de atrair (efeito indutivo captor) ou repelir (efeito indutivo doador)
eletrons.
Efeitos eletrnicos
Efeito indutivo retirador

Efeito retirador de eltrons gerado por grupos com alta
eletronegatividade. Ir tornar a cadeia carbnica a qual se liga
menos densa eletronicamente (deficiente em eltrons). Ex.: -F ; Cl; -Br; -OR; -NH2; -NO2.
1. Tpicos Gerais
CH3 OH
H OH
HO OH
I OH
Br OH
Cl OH
129
pKa
16,6
15,755
11,6
10,6
8,7
4,5
Voc pode ver que tomos ou grupos mais eletronegativos conduzem a

maior acidez, porque eles atraem mais os eltrons e assim liberam com maior facilidade o
+
Efeitos eletrnicos
Efeito indutivo retirador

Os efeitos indutivos enfraquecem medida que a distncia at o
grupo aumenta.
"!
CH3
Cd!
CH3
"!
CH3
"!
CH3
is
more
Cd!
stable
"!
H
CH3
than
indutivo
doador
is
more
stable
than
Cd!
CH3
"!
H
Efeitos
eletrnicos
is
more
C!
stable H
H
than
"!
Efeito
Efeito doadorIsopropyl
de eltrons
grupos
densidade
tert-Butyl cation
cationgerado por
Ethyl
cationcom alta Methyl
cation
(3) (most stable)
(2)
stable)
eletrnica. Ir aumentar
a densidade (1)
eletrnica sob(least
a cadeia
carbnica a qual se liga (tornando-a rica em eltrons).
In summary:
Ex.: -CR3; -CHR2; -CH2R; -CH3.
The relative stability of carbocations is 3 " 2 " 1 " methyl.
This trend is also readily seen in electrostatic potential maps for these carbocations (Fig. 6.8).
(a) tert-Butyl (3)
(b ) Isopropyl (2)
(c ) Ethyl (1)
(d ) Methyl
Figure 6.8 Maps of electrostatic potential for (a) tert-butyl (3), (b) isopropyl (2), (c) ethyl (1),
and (d) methyl carbocations show the trend from greater to lesser delocalization (stabilization) of
the positive charge in these structures. Less blue color indicates greater delocalization of the
positive charge. (The structures are mapped on the same scale of electrostatic potential to allow
direct comparison.)
Efeitos eletrnicos
2) Mesomerismo ou ressonncia- efeito mesomrico.

O efeito mesomrico est relacionado a um processo que chamamos
de deslocalizaao de eltrons.
Free e
Reactants
G =
100 kJ mol1
Freeenergy
change
Efeito estrico
CH3OH + Cl
Products
Figure 6.4 A free-energy

diagram for the reaction of
chloromethane with hydroxide
ion at 60C.
o bloqueio espacial de uma

determinada
regio da molcula realizado
Reaction
coordinate
por grupos volumosos. No exemplo abaixo temos as velocidades relativas

para reaes de substituio nucleoflica em diferentes haletos de alquila
(observe o bloqueio estrico da aproximao do nuclefilo).
6.8 The Stereochemistry of SN2 Reactions

The stereochemistry of SN2 reactions is directly related to key features of the mechanism
that we learned earlier:
!
The nucleophile approaches the substrate carbon from the back side with
respect to the leaving group. In other words, the bond to the nucleophile that is
forming is opposite (at 180) to the bond to the leaving group that is breaking.
Nucleophilic displacement of the leaving group in an SN2 reaction causes inversion of configuration at the substrate carbon.
We depict the inversion process as follows. It is much like the way an umbrella is
inverted in a strong wind.
Transition state for an SN2 reaction.
An inversion of configuration
HO
C
H
Cl
"!
HO
"!
C
H H
Cl
H
HO
C
H
Cl
Aromaticidade
O estudo dos compostos aromticos deu-se em
1825 com a descoberta do benzeno por Faraday.

Substncias como o benzeno so encontradas em leos
produzidos por rvores e outras plantas.

Estas substncias foram chamadas de aromticas, em razo
de seu cheiro agradvel.
Compostos insaturado pouco reativo.
Aromaticidade
O benzeno tem frmula molecular C6H6

Kekul props a seguinte estrutura
para o benzeno:
Em 1930 novas tcnicas de difrao e raios X, mostraram que o
benzeno era uma molcula planar e que as seis ligaes

carbono-carbono tem o mesmo comprimento. Ou seja o benzeno
no tem ligaes duplas e simples alternadas.
O comprimento da ligao carbono-carbono 1,39 A< que uma
ligao simples (1.54 A) e > que uma ligao dupla (1,33 A).
2
2
BenzeneEach
is aof planar
molecule.
Each
of itsneither
six oncarbon
atoms
the six p electrons,
therefore,
is localized
a single carbon
nor is
in asp hybridized. An sp
bond between
two carbons
(as in anangles
alkene). Instead,
each p electron is sharedto
by the
all sixsize of the angles of a
hybridized
carbon
has bond
of 120identical
carbons. The six p electrons are delocalizedthey roam freely within the doughnutAromaticidade
3-D Molecule:
2
sp
planar shaped
hexagon.
Each
of
the
carbons
in
benzene
uses
two
orbitals
to bond to two
clouds that lie over and under the ring of carbon atoms. Consequently, benzene
Benzene
2 containing either dashed lines or a circle, to symbolize
can be represented
by
a hexagon
sp
other carbons;
the
third
orbital overlaps the s orbital of a hydrogen (Figure 7.1a).
the six delocalized p electrons.
Each carbon also has a p orbital at right angles to the sp 2 orbitals. Because benzene is
Ossixeltrons
deslocalizados no anel, em vez de
planar,the
p orbitalsareesto
parallel
or (Figure 7.1b). The p orbitals are close enough for
cada
par de
estar
localizado
entre
doisadjacent
tomoscarbons.
side-to-side
overlap,
so eltrons
each p orbital
overlaps
the p orbitals
on both
de
As a result,
the
overlapping
orbitals
form
continuous
doughnut-shaped cloud of
This
typecarbono.
of representation
makes p
it clear
that there
are noadouble
bonds in benzene.
We see
now that and
Kekuls
structure for
benzene was pretty closecloud
to the correct
strucelectrons
above,
another
doughnut-shaped
of
electrons
below, the plane
ture. The actual structure of benzene is a Kekul structure with delocalized electrons.
of the benzene ring (Figure 7.1c). The electrostatic potential map (Figure 7.1d) shows
that all the carboncarbon bonds have the same electron density.
a.
b.
c.
d.
Each of the six p electrons, therefore, is localized neither on a single carbon nor in a
bond between two carbons (as in an alkene). Instead, each p electron is shared by all six
carbons. The six p electrons are delocalizedthey roam freely within the doughnutshaped clouds that lie over and under the ring of carbon atoms. Consequently, benzene
can be represented by a hexagon containing either dashed lines or a circle, to symbolize
p electrons.
the sixdelocalized
Figure 7.1
(a) The carboncarbon and carbonhydrogen s bonds in benzene.
(b) The p orbital on each carbon of benzene can overlap with two adjacent p orbitals.
(c) The clouds of electrons above and below the plane of the benzene ring.
(d) The electrostatic potential map for benzene.
or
7.3
Resonance Contributors
the Resonance
Hybrid
This type of and
representation
makes
it clear that there are no double bonds in benzene.
We seeA now
that toKekuls
fordelocalized
benzeneelectrons
was pretty
to the correct strucdisadvantage
using dashedstructure
lines to represent
is that theyclose
do
genation.
We
depictthe
this
type of
reaction
E forstituted:
an electrophilic portion
Prob lem 15
.1 Ican
Tell whether
following
compound
s aregenerally,
o rt h o -, rnera-.using
or para-disub
of a reagent and
a nucleophilic
portion, as follows.
(bl
lal Nu
CIYfor
j(C
H3
(e)
Aromaticidade
VC C ! E Nu addition E C C Nu
Estabilidade
do benzeno
lUPAC nam es fo r th e foll owing compounds:
Problem 15.2
Some specific reactions of this type that we shall study in this chapter include addition of
O benzeno extraordinariamente estvel.
hydrogen halides, sulfuric acid, water (in the presence of an acid catalyst), and halogens. Later
Give
lc]
[b)
no
reaes
dethat
adio
dosalkenes.
alcenos.
we shall also study
somesofre
specialized
reagents
undergocaractersticas
addition reactions with
H
(d)
Alkyl halide
(Sections 8.2, 8.3,

BRUI15-593_621r3 27-03-2003 2:51 PM Page 608 and 10.9)
H
(I)
Ie)
CI" 0 CH3
OSO3H
OSO3H
Alkyl hydrogen
sulfate
Problem 15 .3C Draw

C str uct ure s cor resp onding to th e foll owin g IUPAC n am es:
(a) fI-Bromoc h lorobenzene
(b ) p-Brom otolu en e
(c) r-Chloroaniline
(d) l- Chloro-3,.'i -dim elhylb en zen e
H OH
Alkene
15.2
HA
(cat.)
608
CHAPTER 15
(Section 8.4)
OH
Alcohol
8.5) of Benzene
Aromaticity (Section
Reactions
Structure and Stability of Benzene:

Molecular XOrbital
X Theory
X C C X
15.10
Halogenation of Benzene
Dihaloalkane
(Sections
8.12, 8.13)
Alt ho ugh ben zene is clearly unsatu rat ed, it is mu ch more stable
than typical
al keries and fails to undergo the usual a lk ene rea ctions. Cyclohexene, for
The bromination or chlorination of benzene requires a Lewis acid such as fe
ins ta n ce, rea cts rapidly with Br2 and g ives th e addition product 1,2-dibromoor ferric chloride. Recall that a Lewis acid is a compound that accepts a
cycloh exan e, but benzene reacts only slowly wi th Br2 and g ives thmide
e substitution
p roduct C 6HsBr. As a resu lt of thi s substituti on , th e cyclic con jugation
of
theelectrons (Section 1.21).
a pair of
ben zen e ring is retained.
8.1A How to Understand Additions to Alkenes
bromination
Two characteristics of the double bond help us understand why these
addition reactions occur:
H
B
sr
Fe the conversion of one p bond and one s bond (Sections

1. An addition reaction results in
'
+ HB'
catalys t
1.12 and 1.13) into two s bonds. The result of this change
is
4
Br usually energetically + Br
2
H
favorable. The energy released in making two s bonds exceeds that needed to break
IAddition product)
Bromobenzene
one s bondBenzene
and one p bond (because
bonds are weaker),
and, therefore, addition
(substitutionp
product)
NOTformed
reactions are usually exothermic:
FeBr3
Br
+ HBr
bromobenzene
chlorination
We can ge t a qu antitati ve id ea of benzene 's stability by m ea suring h eats of

hy drogenati on (Sec tio n 6.6 ). Cy cl o h exe n e, an isol at ed alk en e, h as Mr'hydrog '"
!and
E 1,3-cyclohexadi
C a con
C juga ted diene, h as
Nu
C ol),
- 118 kl/rn o) (- 28 C
.2 kcal/m
ene,
= - 230 kj /rn ol ( - 55.0 kcal/rnol l. As noted in Secti on 14.1, this va lue
for l, 3- cy cl ohe xadien e is a bit less than twice that forE
cycl oh
exen e becau se conNu
+ Cl2
FeCl3
Cl
+ HCl
Aromaticidade
Estabilidade do benzeno
Ele termodinamicamente mais estvel.
Aromaticidade
Estabilidade do benzeno
Ciclo-exatrieno"
Cicloexa-1,3-dieno
cicloexeno
Essa diferena entre a quantidade de calor

realmente liberada e aquela calculada
chamada de energia de ressonncia.
31 AM Page 268
Aromaticidade
A substncia estabilizada por deslocalizao de
eltrons ou estabilizada por ressonncia.
lectron Delocalization and Resonance More About Molecular Orbital Theory
n by
rrows
( ).
BRUI15-593_621r3 27-03-2003 2:51 PM Page 595
resonance structure. The actual structure with delocalized electrons is called a

resonance hybrid. Notice that it is easy to see that there are six p electrons in the ring
of each resonance contributor.
1
1
2
Section 15.2
Arom
> Figur
a.
b.
c.
resonance hybrid
double-headed arrow does not mean that the structures are in equilibrium with one
have much smaller resonance energies. Compounds such as benzene with unusually
another. Rather, it indicates that the actual structure lies somewhere between
the
large resonance
energies are called aromatic compounds. How can we tell whether a
structures of the resonance contributors. Resonance contributors are merely acompound
conve- is aromatic by looking at its structure? In other words, what structural feanient way to show the p electrons; they do not depict any real electron distribution.
tures do aromatic compounds have in common?
To be
For example, the bond between C-1 and C-2 in benzene is not a double bond,
al-classified as aromatic, a compound must meet both of the following criteria:
It must have an uninterrupted cyclic cloud of p electrons (often called a p

though the resonance contributor on the left implies that it is. Nor is it a single 1.bond,
cloud) above and below the plane of the molecule. Lets look a little more closeas represented by the resonance contributor on the right. Neither of the contributing
ly at what this means:
resonance structures accurately represents the structure of benzene. The actual strucFor the p cloud to be cyclic, the molecule must be cyclic.
ture ofbenzenethe resonance hybridis given by the average of the two resonance
For the p cloud to be uninterrupted, every atom in the ring must have a p
contributors.
orbital.
For the p cloud to form, each p orbital must overlap with the p orbitals on
The following analogy illustrates the difference between resonance contributors and
the resonance hybrid. Imagine that you are trying to describe to a friend what aeither side of it. Therefore, the molecule must be planar.
The p cloud must contain an odd number of pairs of p electrons.
rhinoceros looks like. You might tell your friend that a rhinoceros looks like a2.cross
between a unicorn and a dragon. The unicorn and the dragon dont really exist,Benzene
so theyis an aromatic compound because it is cyclic and planar, every carbon in the
ring
are like the resonance contributors. They are not in equilibrium: A rhinoceros doeshas
nota p orbital, and the p cloud contains three pairs of p electrons.
The German chemist Erich Hckel was the first to recognize that an aromatic comjump back and forth between the two resonance contributors, looking like a unicorn
one
pound must have an odd number of pairs of p electrons. In 1931, he described this
minute and a dragon the next. The rhinoceros is real, so it is like the resonancerequirement
hybrid. by what has come to be known as Hckels rule, or the 4n ! 2 rule. The
Por ter seus eltrons deslocalizados, todas as ligaes C-C tem o

mesmo comprimento (algo entre uma ligao simples e uma dupla);
O benzeno particularmente estvel em virtude de sua energia de
ressonncia extraordinariamente alta 151 KJ/mol.
(a) Each
orbital. (
orbitals
above an
benzene
potentia
that all t
have the
Aromatic
stable.
For a com
it must be
uninterru
P cloud m
pairs of P
solom_c08_331-384hr.qxd
24-09-2009
11:58
Page 332
Aromaticidade
Antes de 1900, os qumicos admitiam que o anel de

Chapter 8 eAlkenes
and Alkynes
II
ligaes simples
duplas
alternadas
era a caracterstica
estrutural que dava origem as propriedades aromticas.
8.1 Addition Reactions of Alkenes
Em 1911, Richard
Willstter
sintetizou
o ciclo-octatetraeno.
We have already
studied one addition
reaction of alkeneshydrogenationin
which a
332
hydrogen atom is added at each end of a double (or triple) bond. In this chapter we shall
study other alkene addition reactions that do not involve the same mechanism as hydrogenation. We can depict this type of reaction generally, using E for an electrophilic portion
of a reagent and Nu for a nucleophilic portion, as follows.
C
C !E
Nu
addition
Nu
Some specific reactions of this type that we shall study in this chapter include addition of
hydrogen halides, sulfuric acid, water (in the presence of an acid catalyst), and halogens. Later
we shall also study some specialized reagents that undergo addition reactions with alkenes.
H
OSO3H
OSO3H
Alkyl hydrogen
sulfate
(Section 8.4)
Alkene
Alkyl halide
(Sections 8.2, 8.3,

and 10.9)
OH
HA (cat.)
OH
Alcohol
(Section 8.5)
Dihaloalkane
(Sections 8.12, 8.13)
8.1A How to Understand Additions to Alkenes
Aromaticidade
Critrios para a aromaticidade

1. Para ser classificada como aromtica, uma substncia
deve atender aos seguintes critrios:
Ela deve ter uma nuvem cclica e ininterrupta de eltrons
acima e abaixo do plano da molcula.
Para nuvem ser cclica, a molcula

deve ser cclica.
BRUI07-263_297r4 21-03-2003 11:31 AM Page 269
Para a nuvem ser ininterrupta, todo tomo do anel deve ter um orpital p.
Para se formar a nuvem , cada orbital p deve sobrepor-se aos orbitais
BRUI15-593_621r3 27-03-2003 2:51 PM Page 595
p de cada lado da nuvem. Portanto a molcula tem que ser planar.

Section 15.2
Aromatic Hydrocarbons
595
Section 7.4
Draw
> Figure 15.1
a.
b.
(a) Each carbon of benzene has a p

orbital. (b) The overlap of the p
orbitals forms a cloud of p electrons
above and below the plane of the
benzene ring. (c) The electrostatic
potential map for benzene shows
thatno
alloverlap
the carboncarbon bonds
have the same electron density. cyclooctatetraene
c.
7.4
Drawing Resonance Contributors
have much smaller resonance energies. Compounds such as benzene with unusually
We have seen that an organic compound with delocalized electrons is generally reprelarge resonance energies are called aromatic compounds. How can we tell whether a
sented as a structure with localized electrons, so that we will know how many p eleccompound is aromatic by looking at its structure? In other words, what structural featrons areAromatic
presentcompounds
in the molecule.
For example, nitroethane is represented as having a
are particularly
tures do aromatic compounds have in common?
nitrogenoxygen
double bond and a nitrogenoxygen single bond.
stable.
To be classified as aromatic, a compound must meet both of the following criteria:
O
1. It must have an uninterrupted cyclic cloud of p electrons (often called a p
+
cloud) above and below the plane of the molecule. Lets look a little more closeCH3CH2 N
ly at what this means:
O
For the p cloud to be cyclic, the molecule must be cyclic.
nitroethane
For the p cloud to be uninterrupted, every atom in the ring must have a p
However, the two nitrogenoxygen bonds in nitroethane are identical; they each have
orbital.
Aromaticidade
Critrios para a aromaticidade

2.
A nuvem deve conter um nmero mpar de pares

eltrons .
O fsico alemo Erich Huckel foi o primeiro a reconhecer que uma
substncia aromtica deve ter um nmero mpar de pares de

eltrons.
A regra de Huckel: determina que para uma substncia

cclica planar ser aromtica, sua nuvem ininterrupta
deve conter (4n +2) eltrons , onde n um nmero
inteiro qualquer.
BRUI07-263_297r4 21-03-2003 11:31 AM Page 269
no overlap
cyclooctatetraene
7.4
Drawing Resonance Contributor
Hidrocarbonetos aromticos
Hidrocarbonetos monocclicos com ligaes simples e duplas
alternadas so chamados de anulenos.

O tamanho do anel de um anuleno indicado por um nmero
entre colchetes.
1.17 How to Interpret and Write Structural Formulas

Organic chemists use a variety of ways to write structural formulas. The most common types
of representations are shown in Fig. 1.37 using propyl alcohol as an example. The dot structure shows all of the valence electrons, but writing it is tedious and time-consuming. The
other representations are more convenient and are, therefore, more often used.
Sometimes we even omit unshared pairs when we write formulas. However, when we
write chemical reactions, we see that it is necessary to include the unshared electron pairs
when they participate in the reaction. It is a good idea, therefore, to get into the habit of
writing the unshared (nonbonding) electron pairs in the structures you draw.
Representao das molculas

H H H
H C C C O H
H H H
Modelo
de bola e model
vareta
Ball-and-stick
(a)
Estrutura
de pontos
Dot formula
(b)
Frmula
traos
Dashde
formula
(c)
CH3CH2CH2OH
Frmula
condensada
em basto
Bond-line formula
Condensed
formula Estrutura
(e)
(d)
Figure 1.37 Structural formulas for propyl alcohol.
1.17A Dash Structural Formulas

If we look at the model for propyl alcohol given in Fig. 1.37a and compare it with the dot,
dash, and condensed formulas in Figs. 1.37bd we find that the chain of atoms is straight
in those formulas. In the model, which corresponds more accurately to the actual shape of
the molecule, the chain of atoms is not at all straight. Also of importance is this: Atoms
joined by single bonds can rotate relatively freely with respect to one another. (We discussed this point briefly in Section 1.12B.) This relatively free rotation means that the chain
of atoms in propyl alcohol can assume a variety of arrangements like these:
H
H
H
C
H
H
C
O
or
H
C
H
C
H
H
or
OH
H
C
H
O
Ball-and-stick model
(a)
Dot formula
(b)
Dash formula
(c)
Condensed formula
(d)
Bond-line formula
(e)
Figure 1.37 Structural formulas for propyl alcohol.
1.17A Dash Structural Formulas
01_001-052hr1.qxd
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14:21
Page 42
If we look at the model for propyl alcohol given in Fig. 1.37a and compare it with the dot,
dash, and condensed formulas in Figs. 1.37bd we find that the chain of atoms is straight
in those formulas. In the model, which corresponds more accurately to the actual shape of
the molecule, the chain of atoms is not at all straight. Also of importance is this: Atoms
joined by single bonds can rotate relatively freely with respect to one another. (We discussed this point briefly in Section 1.12B.) This relatively free rotation means that the chain
of atoms in propyl alcohol can assume a variety of arrangements like these:
H
H
H
O
H
H
H
H
H
H
H
H
Chapter 1 The BasicsBonding and Molecular Structure
H or
C
C
C
C
C
or
O
H
O
H
H
H
C
(Propyl alcohol does Cnot have 90 bond angles.CIt has tetrahedral C
bond angles.)
Dash strucH
H
H
H
H what
H is called the connectivity
H
H
tural formulas show
of the atoms. Constitutional isomers
42
Helpful Hint
It is important that you be able to
recognize when a set of structural
formulas has the same connectivity
versus when they are constitutional
isomers.
Equivalent dash formulas for propyl alcohol

(Section 1.3A) have different
connectivities and, therefore, must have different structural
formulas. It also means that all of the structural formulas above are equivalent and all represent
propyl
Dash structural
formulas such
as thesewhose
indicate formula
the way in which
the atoms
Consider
thealcohol.
compound
called isopropyl
alcohol,
we might
write in a
are attached to each other and are not representations of the actual shapes of the molecule.
variety of ways:
H
O9H
H 9 C 9 C 9 C 9 H or H 9 C 9 C 9 C 9 H or H 9 C 9 C 9 H
H
O
H
H
H9C9H
H
Equivalent dash formulas for isopropyl alcohol
Isopropyl alcohol is a constitutional isomer (Section 1.3A) of propyl alcohol because its
atoms are connected in a different order and both compounds have the same molecular formula, C3H8O. In isopropyl alcohol the OH group is attached to the central carbon; in propyl
alcohol it is attached to an end carbon.
!
In problems you will often be asked to write structural formulas for all the isomers
that have a given molecular formula. Do not make the error of writing several
equivalent formulas, like those that we have just shown, mistaking them for different constitutional isomers.
Review Problem 1.20
There are actually three constitutional isomers with the molecular formula C3H8O. We have
seen two of them in propyl alcohol and isopropyl alcohol. Write a dash formula for the third
isomer.
1.17B Condensed Structural Formulas
Condensed structural formulas are somewhat faster to write than dash formulas and, when
we become familiar with them, they will impart all the information that is contained in the
dash structure. In condensed formulas all of the hydrogen atoms that are attached to a particular carbon are usually written immediately after the carbon. In fully condensed formulas, all of the atoms that are attached to the carbon are usually written immediately after
that carbon, listing hydrogens first. For example,
Cl
CH3CHCH2CH3 or CH3CHClCH2CH3
Cl
Condensed formulas
Dash formula
The condensed formula for isopropyl alcohol can be written in four different ways:
H
Dash formula
CH3CHCH3 or CH3CH(OH)CH3
H
OH
CH3CHOHCH3 or (CH3)2CHOH
Condensed formulas
Chapter 1
solid or dashed wedges. Consider the following examples of molecules depicted by bondline formulas.
Bond-line
formulas
CH3 CH2
CH3CHClCH2CH3 !
CH
CH3 !
Cl
Cl
CH3 CH2
CH3CH(CH3)CH2CH3 !
CH
CH3 !
CH3
Helpful Hint
CH3 CH2
s you become more familiar with

organic molecules, you will find
bond-line formulas to be very
useful tools for representing
structures.
(CH3)2NCH2CH3 !
CH3 !
CH3
Bond-line formulas are easy to draw for molecules with multiple bonds and for cyclic
molecules, as well. The following are some examples.
CH2
H2C9CH2
and
H2C9CH2
H2C9CH2
As you become more familiar with

organic molecules, you will find
bond-line formulas to be very
useful tools for representing
structures.
(CH3)2NCH2CH3 !
CH3 !
CH3
Bond-line formulas are easy to draw for molecules with multiple bonds and for cyclic
molecules, as well. The following are some examples.
H2C9CH2
and
CH3
CH
"
CH2
CH3
CH2
CH3
CH2" CHCH2OH !
OH
H2C9CH2
H2C9CH2
01_001-052hr1.qxd
14-10-2009
14:21
Page 46

46
Chapter 1
Frmulas
are used. Note that
when usingTridimensionais
bond-line formulas we continue to omit hydrogen atoms
unless they are relevant to clarifying the three-dimensional perspective of some other group.
Figure 1.38 shows some examples of three-dimensional formulas.
H
H C
H
H
H
H
HH
or
C
H
H
etc.
C
H
H C
H
Br
Ethane
Figure 1.38 Some

examples of threedimensional formulas.
OH
Br
H
H
or
H C
H
etc.
H OH
HO
Br
H
Examples of bond-line formulas that

include three-dimensional representations
Review Problem 1.25
or
Bromomethane
Br
H
Br
Br
An example involving trigonal
planar geometry
An example involving
linear geometry
Write three-dimensional (wedgedashed wedgeline) representations for each of the

following:
(a) CH3Cl
(b) CH2Cl2
(c) CH2BrCl
(d) CH3CH2Cl
HHHHHHH H
H C C C C C C C C H
HHHHHHH H
H H H H H H H H
H C C C C C C C C H
H H H H H H H H
Frmula de pontos
ou de Lewis
Frmula de traos
ou de Kekul
CH3CH2CH2CH2CH2CH2CH2CH3
Frmula condensada
Frmula de linhas
H
H C
H
H
C
H
H H
C C
OH H
H
C H
H
H
H H
H C C C C C Br
H H
H
H H
H C
C H
C
H C
H
H C C
H
H
ou
OH
ou
ou
Br
ISOMERIA CONSTITUCIONAL
CH3CH2CH2CH3
CH3CH2OH
CH3
CH3CHCH3
CH3-O-CH3
Compostos com frmula C4H10O:

OH
OH
OH

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Universidade Federal do Cear

Introduo s molculas orgnicas

teoria da fora vital (sculo IX).

gordura, s poderiam ser sintetizados por organismos vivos.

SUBSTNCIAS ORGNICAS: Derivadas de

O nome qumica orgnica pr

Esquema 1.1.1. Sntese

primeira vista, a diviso

1.1 We Are Stardust

1.1A Development of the Science of Organic Chemistry

Introduo s molculas orgnicas

O carbono no libera nem aceita eltrons prontamente.

View Article Online

O carbono compartilha eltrons com outros tomos de

carbono bem como com diferentes tipos de tomos.

Marine natural products - Natural Product Reports (RSC Publishin...

Introduo s molculas orgnicas

View Article Online

Introduo s molculas orgnicas

Quando estudamos qumica orgnica, avaliamos como as

substncias orgnicas reagem.

Ligao qumica eltrons atmos

Um tomo consiste de um ncleo denso (nutrons e

prtons), positivamente carregado e de eltrons

nuvem de densidade varivel; uma maior densidade da nuvem

Onde a nuvem tem maior densidade a

Fatia do orbital 1s cortada no plano xy

Figura 1.2.4. Visualizao do orbital

Observao: a curva e a nuvem de pontos apresentadas na figura aci

Os nmeros qunticos so usados para descrever um

Nmero quntico principal

# FIGURE 6.19 Comparison of the 1s,

Estrutura atmica- Orbital atmico

O nmero quntico secundrio ou azimuthal (l). Refere-se ao

formatos dos orbitais.

O nmero quntico magntico (ml). Esse nmero quntico

fornece a orientao do orbital no espao.

(Aufbau is German for building up.)

(orbitais de mesma energia), If

Figure 1.7 The ground state electron configurations of some second-row

O estudante certamente j conhece a seqncia de preenchimento dos

Flor (nmero atmico 9)

Figura 1.2.5. Seqncia de preenchimento de orbitais

H ainda a considerar que dentro de um mesmo sub-nvel com vrios

nmero quntico secundrio, com ndices (x, y, z, etc

Figure 1.8 The potential energy of the

Os orbitais atmicos so designados pelas letras s, p d

! FIGURE 6.21 Probability density [C(r )] 2 in the 1s, 2s, and 3s

RELATED EXERCISES: 6.50, 6.59, 6.60, and 6.91

orbitals. The subscript on the orbital label

atravs dela que muitas das propriedades das

Lewis mostrou que a falta de reatividade dos gases

nobres (grupo 8 A) indica um alto grau de estabilidade em

ximum of two electrons may be placed in each orbital

Remember: One definition of electronegativity

199: (negative end)

Because the hydrogen chloride molecule has

figurations of some second-row elements.

Dipole moment $ charge (in esu) # distance (in cm)

atively far apart their total energy is simply that of

n HCl, for example,

tomo para outro, criando ons positivos (ctions) e negativos

artial negative charge on the oxygen atom in a C O bond. The bond