1.

Estructura , Enlaces
Compuestos Orgnicos
Qumica Orgnica
2
Qumica Orgnica
Rama de la qumica que se dedica al
estudio de los compuestos de carbono.
El nmero de compuestos orgnicos
naturales y sintticos conocidos en la
actualidad sobrepasa los diez millones.
3
Elementos ms importantes en
los compuestos orgnicos:
El hidrgeno, carbono, nitrgeno y oxgeno
constituyen el 99.33 % de todos los tomos que
forman los compuestos orgnicos.
Carbono Hidrgeno Oxgeno Nitrgeno
Azufre Fsforo Cloro Flor
Yodo Magnesio Molibdeno Hierro
4
Organic Compounds
Typically, organic compounds
Contain carbon.
Have covalent bonds.
Have low melting points.
Have low boiling points.
Are flammable.
Are soluble in nonpolar
solvents.
5
Qumica Orgnica
Organic until mid 1800s referred to compounds
from living sources (mineral sources were
inorganic)
Whler in 1828 showed that urea, an organic
compound, could be made from a non-living source:
6
Organic Chemistry
Today, organic compounds are those
based on carbon structures and
organic chemistry studies their
structures and reactions
Includes biological molecules, drugs,
solvents, dyes, food additives, pesticides,
and others.
Does not include metal carbonate salts and
other simple ionic compounds (inorganic)
7
Other Covalent Bonds
Carbon atoms form bonds mostly
with H and other C atoms, but also
with atoms of O, N, S, and halogens
F, Cl, and Br.
8
Conectividad de los principales tomos
presentes en familias orgnicas
C--- 4
H--- 1
O--- 2
N--- 3
X--- 1
Conectividad=
No. De enlaces
que forman
9
Organic Chemistry
10
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
sp
3
-Hybridization of carbon
Figure 1.20
11
Tetrahedral Carbon:
12
sp
3
Hybridization
13
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Orbital overlaps involved in bonds of methane
Figure 1.22
14
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Orbital overlap descri ption
Figure 1.23
15
Tetrahedral Structure of
Methane
sp
3
orbitals on C overlap with 1s
orbitals on 4 H atom to form four
identical C-H bonds
Each CH bond has a strength of
438 kJ /mol and length of 110 pm
Bond angle: each HCH is
109.5, the tetrahedral angle.
16
Tetrahedral Structure of
Methane
17
Hybridization: sp
3
Orbitals and
the Structure of Ethane
Two Cs bond to each other by overlap of an sp
3
orbital from each
Three sp
3
orbitals on each C overlap with H 1s
orbitals to form six CH bonds
18
Hybridization: sp
3
Orbitals and
the Structure of Ethane
CH bond
strength in
ethane 420
kJ /mol
CC bond is 154
pm long and
strength is 376
kJ /mol
All bond angles
of ethane are
tetrahedral
19
Hybridization: sp
2
Orbitals and
the Structure of Ethylene
20
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
sp
2
-Hybridization of carbon
Figure 1.25
21
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Atoms of ethylene
Figure 1.24
22
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Orbital overlaps and
bonding in ethylene
Figure 1.27
23
Hybridization: sp
2
Orbitals and
the Structure of Ethylene
sp
2
hybrid
orbitals: 2s orbital
combines with two
2p orbitals, giving 3
orbitals (spp = sp
2
)
sp
2
orbitals are in a
plane with120
angles
Remaining p orbital
is perpendicular to
the plane
90
120
24
Bonds From sp
2
Hybrid
Orbitals
Two sp
2
-hybridized orbitals overlap to form a
bond
p orbitals overlap side-to-side to formation a
pi () bond
sp
2
sp
2
bond and 2p2p bond result in
sharing four electrons and formation of C-C
double bond
Electrons in the bond are centered between
nuclei
Electrons in the bond occupy regions are on
either side of a line between nuclei
25
Bonds From sp
2
Hybrid Orbitals
26
Structure of Ethylene
H atoms form bonds with four sp
2
orbitals
HCH and HCC bond angles of about 120
CC double bond in ethylene shorter and stronger
than single bond in ethane
Ethylene C=C bond length 133 pm (CC 154 pm)
27
Hybridization: spOrbitals and the
Structure of Acetylene
C-C a triple bond sharing six electrons
28
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
sp-Hybridization of carbon
Figure 1.29
29
Hybridization: spOrbitals and the
Structure of Acetylene
Carbon 2s orbital hybridizes with a single p orbital
giving two sp hybrids (two p orbitals remain
unchanged)
sp orbitals are linear, 180 apart on x-axis
Two p orbitals are perpendicular on the y-axis and
the z-axis
30
Orbitals of Acetylene
Two sp hybrid orbitals from each C form spsp
bond
p
z
orbitals from each C form a p
z
p
z
bond by
sideways overlap and p
y
orbitals overlap similarly
31
Bonding in Acetylene
Sharing of six electrons forms C C
Two sp orbitals form bonds with hydrogens
32
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Acetylene is a linear molecule
Figure 1.28
33
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Orbital overlaps and bonding in acetylene
Figure 1.31
34
Repaso
35
Figure 11.9 The bonds in ethane(C
2
H
6
).
both C are sp
3
hybridized
s-sp
3
overlaps to bonds
sp
3
-sp
3
overlap to form a bond
relatively even
distribution of electron
density over all
bonds
36
Figure 11.10
The and bonds in ethylene (C
2
H
4
).
overlap in one position -
p overlap -
electron density
37
Figure 11.11
The and bonds in acetylene (C
2
H
2
).
overlap in one position -
p overlap -
38
Figure 11.12
Electron density and bond order.
39
Multiple Covalent Bonds
Ethylene has a double bond in its Lewis
structure.
VSEPR says trigonal planar at carbon.
40
Ethylene
41
Acetylene
Acetylene, C
2
H
2
, has a triple bond.
VSEPR says linear at carbon.
42
SAMPLE PROBLEM 11.2 Describing the Bond in Molecules
SOLUTION:
PROBLEM: Describe the types of bonds and orbitals in acetone, (CH
3
)
2
CO.
PLAN: Use the Lewis structures to ascertain the arrangement of groups and
shape at each central atom. Postulate the hybrid orbitals taking note of
the multiple bonds and their orbital overlaps.
sp
3
hybridized
sp
3
hybridized
sp
2
hybridized
bonds
bond
43
Figure 11.13
Restricted rotation of -bonded molecules in C
2
H
2
Cl
2
.
CIS TRANS
44
10.5
45
Sigma () and Pi Bonds ()
Single bond
1 sigma bond
Double bond
1 sigma bond and 1 pi bond
Triple bond 1 sigma bond and 2 pi bonds
How many and bonds are in the acetic acid
(vinegar) molecule CH
3
COOH?
C
H
H
C H
O
O H
bonds = 6 + 1 = 7
bonds = 1
10.5
46
Delocalized molecular orbitals are not confined between
two adjacent bonding atoms, but actually extend over three
or more atoms.
10.8
47
Comparison of C-C & C-H bonds:
48
Comparison of C-H bonds:
Molecule Bond Energy (kcal) Length (pm)
Ethane
C
sp3
-H 100 110
Ethylene
C
sp2
-H 106 108
Acetylene
C
sp
-H 132 106
49
Comparison of C-C bonds:
Molecule Bond Energy (kcal) Length (pm)
Ethane
C
sp3
-C
sp3
90 154
Ethylene
C
sp2
-C
sp2
146 133
Acetylene
C
sp
-C
sp
200 120
50
Molecular Formulas?
51
Shape & Hybridization? Prob. :
52
Hybridizations & Lone Pairs
Prob.
53
Hybridization & Geometry
Prob.
54
Hybridization of Nitrogen and
Oxygen
Elements other than C can
have hybridized orbitals
HNH bond angle in
ammonia (NH
3
) 107.3
Ns orbitals (sppp) hybridize to
form four sp
3
orbitals
One sp
3
orbital is occupied by
two nonbonding electrons, and
three sp
3
orbitals have one
electron each, forming bonds
to H
Elements other than C can
have hybridized orbitals
HNH bond angle in
ammonia (NH
3
) 107.3
Ns orbitals (sppp) hybridize to
form four sp
3
orbitals
One sp
3
orbital is occupied by
two nonbonding electrons, and
three sp
3
orbitals have one
electron each, forming bonds
to H
55
Hybridization of Oxygen in
Water
The oxygen atom is sp
3
-hybridized
Oxygen has six valence-shell electrons but forms only
two covalent bonds, leaving two lone pairs
The HOH bond angle is 104.5
56
Summary
Sigma () bonds - Circular cross-section and are formed by
head-on interaction
Pi () bonds dumbbell shape from sideways interaction of
p orbitals
Carbon uses hybrid orbitals to form bonds in organic molecules.
In single bonds with tetrahedral geometry, carbon has four sp
3
hybrid orbitals
In double bonds with planar geometry, carbon uses three
equivalent sp
2
hybrid orbitals and one unhybridized p orbital
Carbon uses two equivalent sphybrid orbitals to form a triple
bond with linear geometry, with two unhybridized p orbitals
Atoms such as nitrogen and oxygen hybridize to form strong,
oriented bonds
The nitrogen atom in ammonia and the oxygen atom in water are
sp
3
-hybridized
57
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Molecular models of methane
Figure 1.7
58
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
A wedge-and-dash drawing of the structure
of methane
Figure 1.8
59
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Shape of a molecule in terms of its atoms
Figure 1.9
60
2.6
61
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Representations of the trigonal planar geometry
of boron trifluoride
Figure 1.10
62
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Models of formaldehyde showing the trigonal planar
geometry of the bonds to carbon
Figure 1.11
63
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Linear geometry of carbon dioxide
Figure 1.12
64
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Contribution of individual bond dipole moments to
molecular dipole moments
Figure 1.13
65
Polarity of Organic Molecules
The covalent bonds C-C and C-H are
nonpolar.
Covalent bonds in which C bonds with O,
N, F, Cl, or Br are polar.
Organic molecules are nonpolar when
dipoles cancel and polar when dipoles
do not cancel.
66
ALCANOS
HIDROCARBUROS
C-C C sp
3
ALQUINOS
CC
C sp
C
n
H
2n+2
ALQUENOS
C=C C sp
2
C
n
H
2n
C
n
H
2n-2
C H
CH
3
CH
3
C=CH
2
H
(R)-(+)-limoneno
CH
3
CH=CH-CC-C C-CC-CH=CH-CH=CH
2
triino aislado de la planta Carthamus tinctorius, defensa
qumica contra la infestacin por nemtodos
CH
3
-(CH
2
)
5
-CH
3
heptano: aceite de pino
CH
3
-(CH
2
)
29
-CH
3
eneitriacontano: cera de abejas
ALIFATICOS
67
FUENTE DE HIDROCARBUROS
PETROLEO
Mezcla compleja de hidrocarburos que se form
a travs del tiempo por descomposicin de
materiales vegetales y animales
CRUDO Lquido negro viscoso que se
encuentra entre rocas
sedimentarias subterrneas
(2000 m)
petro: roca
oleo: aceite
Se extrae excavando la piedra
y bombeando el lquido hacia
la superficie
68
REFINACION DE PETROLEO
Separacin de sus componentes
y transformacin de los menos
voltiles en compuestos ms
pequeos con mayor aplicacin
El primer paso en la refinacin es la destilacin
69
DESTILACION
Destilacin simple
Destilacin fraccionada
70
REFINACIN DEL PETROLEO
Calentamiento a 400C
71
Fracci n Temp. desti l aci n
(C)
Nmero de carbonos
Gas
< 20
C
1
-C
4
Eter de petr l eo 20 - 40 C
5
-C
6
Li gr ona (naf ta l i gera) 60-90 C
6
-C
7
Naft a natural 85-200 C
6
-C
12
y ci cl oal canos
Kerosn 200-300 C
12
-C
15
y aromti cos
Gasoi l 300-400 C
12
y superi ores
Acei te l ubri cante l qui dos no vol t i l es
> C
12
, cadenas l argas
y ci cl os
Asfal t o o coque de
petr l eo
sl i dos no vol ti l es C
16
-C
44
, pol i ci cl os
PETROLEO
72
USOS DE HIDROCARBUROS
Fracciones voltiles: nafta combustible en motores de autos
kerosn combustible en motores a reaccin,
aviones, cohetes. Calefaccin
gasoil combustible en motores Diesel.
Calefaccin
aceite lubricante motores, y pueden separarse ceras
slidas por enfriamiento llamadas
ceras parafnicas y vaselina
asfalto carreteras e impermeabilizacin de
techos
coque combustible
73
CRAQUEO
La fraccin de naftas es slo el 25% del crudo
Es la ms valiosa como combustible y materia prima
de industria petroqumica
El craqueo (cracking) es el proceso por el cual las molculas de las fracciones
de alto punto de ebullicin se rompen y dan productos de cadenas ms
cortas, esto aumenta el rendimiento de nafta a partir de petrleo
C
10
H
22
C
5
H
12
+ C
5
H
10
C
8
H
18
+ C
2
H
4
C
2
H
6
+ C
8
H
16
C
4
H
10
+ C
4
H
8
+ C
2
H
4
alcano alqueno
Etileno: materia prima de
polietileno
74
OCTANAJE
Hidrocarburos ramificados se encienden suavemente en el motor y producen
el desplazamiento del pistn en forma pareja.
Los hidrocarburos lineales tienden a explotar en el cilindro, empujan el pistn
violentamente y se producen golpes
Octanaje: escala arbitraria para evaluar las propiedades de dar golpes de las
naftas
El isooctano es un excelente combustible
muy ramificado. Se le asigna el valor de 100
CH
3
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
3
Al heptano, malo como combustible se le
asigna valor 0
La nafta comn con un octanaje de 87 produce el mismo efecto que una
mezcla de 87% de isooctano y 13% de heptano
CH
3
C CH
2
CH CH
3
CH
3
CH
3
CH
3
isooctano
75
Para aumentar el octanaje se puede agregar etanol o tetraetilplomo
como agente antiknock
(CH
3
CH
2
)
4
Pb
Poderoso neurotxico
En pequeas cantidades
produce retardo mental
en nios
Patente
EPA: 1970
MTBE
CH
3
C O CH
3
CH
3
CH
3
Metilterbutilter
Muy eficiente: 2%
Nafta oxigenada reduce la formacin
de ozono y el smog
Se aument su proporcin a 10% en
los 90 : contaminacin de aguas
Se volvi a bajar a 2%
CH
3
CH
2
OH
Caro
Tiene que mezclarse
con la nafta en la
estacin de servicio
porque tiende a
separarse de los
hidrocarburos
76
PROPIEDADES DE LOS HIDROCARBUROS ALIFATICOS
Punto de fusin Punto de ebullicin Aumentan regularmente con el PM
Disminuyen con la ramificacin
pentano -129,7 36,1
hexano - 95,0 68,9
heptano - 90,0 98,4
octano - 56,8 125,7
isopentano -159,9 27,85
isoctano -107,4 99,3
densidad
alcano P.F. P.E.
hidrocarburo
agua
0,6603
0,6837
0,7025
0,6919
0,6262
0,6201
77
Clasificacin de los compuestos
orgnicos
Los compuestos orgnicos se han
clasificado con base a un conjunto de
tomos (grupo funcional) que los
caracterizan y del cual dependen en
gran medida sus propiedades fsicas y
qumicas.
78
Clasificacin de los compuestos
orgnicos
Compuesto
Grupo
Funcional
Alcanos R-H
Alquenos R-C=C- R
Alquinos R-CC- R
Halogenuros de
alquilo
R-X en donde X=Halgeno
y R =alquilo
Alcoholes R-OH
Aldehdos R-CH=O
Cetonas
R-C-R

O
Compuesto
Grupo
Funcional
teres R-O-R
cidos carboxlicos
R-C=O

OH
steres
R-C=O

O - R
Amidas
R-C=O

NH
2
Aminas R - NH
2