CH 01

1
Introduction to
Organic
Chemistry
2 ed
William H. Brown
1-1
Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved.
1
Covalent
Bonding &
Shapes of
Molecules
Chapter 1
1-2
1 Organic Chemistry
• The study of the compounds of carbon
• Over 10 million organic compounds have been
identified
• about 1000 new ones are discovered or synthesized
and identified each day!
• C is a small atom
• it forms single, double, and triple bonds
• it is intermediate in electronegativity (2.5)
• it forms strong bonds with C, H, O, N, and some metals
1-3
1 Electronic Structure of Atoms
• Structure of atoms
• small dense nucleus,
diameter 10-14 - 10-15 m,
which contains most of
the mass of the atom
• extranuclear space,
diameter 10-10 m, which
contains positively-
charged electrons
1-4
• Electrons are confined to regions of space
called principle energy levels (shells)
• each shell can hold 2n2 electrons (n = 1,2,3,4......)
Number of Relative Energies

Electrons Shell of Electrons
Shell Can Hold in These Shells
4 32 higher
3 18
2 8
1 2 lower
1-5
• Shells are divided into subshells called orbitals,
which are designated by the letters s, p, d,........
• s (one per shell)
• p (set of three per shell 2 and higher)
• d (set of five per shell 3 and higher) .....
Shell Orbitals Contained in That Shell

3 3s, 3p x, 3py, 3p z, plus five 3d orbitals
2 2s, 2p x, 2py, 2p z
1 1s
1-6
1 Shapes of Atomic Orbitals
z
• All s orbitals have the
shape of a sphere, y
with its center at the x
nucleus. Of the s z
orbitals, a 1s is the
smallest, a 2s is larger, an s orbital
and a 3s is larger still y
• A p orbital consists of x
two lobes arranged in
a straight line with the
center at the nucleus
a pz orbital
1-7
1 Electron Structure of Atoms
Rule 1: Orbitals fill in order of increasing energy,
from lowest to highest
Rule 2: Each orbital can hold up to two electrons
Rule 3: When orbitals of equivalent energy are
available but there are not enough electrons to
fill them completely, one electron is added to
each equivalent orbital before a second is added
to any one of them
1-8
1 Lewis Structures
• Gilbert N. Lewis
• Valence shell: the outermost electron shell of an
atom
• Valence electrons: electrons in the valence shell
of an atom; these electrons are used in forming
chemical bonds
• Lewis structure
• the symbol of the atom represents the nucleus and all
inner shell electrons
• dots represent valence electrons
1-9
1 Lewis Structures
• Lewis structures for elements 1-18 of the periodic table
IA IIA IIIA IVA VA VIA VIIA VIIIA
••
H• He
• • • • • ••
••
••
••
••
••
• •N O F Ne
••
••
Li•
••
••
••
Be B C • • •• ••
• • • • • ••
••
••
S• Ar
••
••
•P
••
••
••
••
Al
••
Na • Mg
••
• Si Cl
• •• ••
1-10
1 Lewis Model of Bonding
• Atoms bond together so that each atom in the
bond acquires the electron configuration of the
noble gas closest it in atomic number
• an atom that gains electrons becomes an anion
• an atom that loses electrons becomes a cation
• Ionic bond: a chemical bond resulting from the
electrostatic attraction of an anion and a cation
• Covalent bond: a chemical bond resulting from
two atoms sharing one or more pairs of electrons
1-11
1 Electronegativity
• Electronegativity: a measure of the force of an
atom’s attraction for the electrons it shares in a
chemical bond with another atom
• Pauling scale
• increases from left to right within a period
• increases from bottom to top in a group
+ -
H Cl
2.1 3.0
1-12
1 Electronegativity
Classification of chemical bonds
Difference in
Electronegativity
Between Bonded Atoms Type of Bond
less than 0.5 nonpolar covalent
0.5 to 1.9 polar covalent
greater than 1.9 ionic
1-13
1 Lewis Structures
• To write a Lewis structure
• determine the number of valence electrons in the
molecule or ion
• determine the arrangement of atoms
• connect the atoms by single bonds
• arrange the remaining electrons so that each atom has
a complete valence shell
• show bonding electrons as a single bond
• show nonbonding electrons as a pair of dots
• atoms share 1 pair of electrons in a single bond, 2
pairs in a double bond, and 3 pairs in a triple bond
1-14
1 Lewis Structures
H O H H Cl
H2O (8) HCl (8)
Water Hydrogen chloride
H
H C H H N H
H H
CH4 (8) NH3 (8)
Methane Ammonia
1-15
1 Lewis Structures
H C C H
C2H2 (10)
Acetylene
O
H H H
C C C O H C H
O O
H H H
C2H4 (12) CH2O (12) H2CO3 (24)
Ethylene Methanal Carbonic acid 1-16
1 Lewis Structures
• In neutral molecules containing C, H, N, O, and
halogen
• hydrogen has one bond
• carbon has 4 bonds and no unshared electrons
• nitrogen has 3 bonds and 1 unshared pair of electrons
• oxygen has 2 bonds and 2 unshared pairs of electrons
• halogen has 1 bond and 3 unshared pairs of electrons
1-17
1 Formal Charge
• Formal charge: the charge on an atom in a
molecule or polyatomic ion
• write a Lewis structure for the molecule or ion
• assign each atom all of its unshared (nonbonding)
electrons and one-half its shared (bonding) electrons
• compare this number with the number of valence
electrons in the neutral, unbonded atom
# of valence all one half
Formal=
electrons in unshared + of all shared
charge
unbonded atom electrons electrons
1-18
1 Formal Charge
# of valence all one half
Formal=
electrons in unshared + of all shared
charge
unbonded atom electrons electrons
• if the number assigned to the bonded atom is less than

that assigned to the unbonded atom, the atom has a
positive formal charge
• if the number is greater, the atom has a negative
formal charge
1-19
1 Formal Charge
• Example: draw Lewis structures and show all
formal charges for these ions
NH4 + CH3 NH3 + CH3 OH2 +
OH - HCO3 - CO3 2-
CH3 - CH3 CO2 - BF 4 -
1-20
1 VSEPR Model
H
- •• ••
4 regions of e density
••
C N O
(tetrahedral, 109.5°) H H H H H
H H H
H H H
3 regions of e - density ••
••
(trigonal planar, 120°) C C C O
H H H
2 regions of e - density •• ••
O C O H C C H
(linear, 180°) •• ••
1-21
1 VSEPR Model
Example: predict all bond angles for these
molecules and ions
NH4 + CH3 NH2 CH3 OH
CH3 CH=CH 2 H2 CO3 HCO3 -
CH3 CHO CH3 CO2 H BF 4 -
1-22
1 Polar & Nonpolar Molecules
• A molecule is polar if
• it has polar bonds and
• its center of positive charge is at a different place
than its center of negative charge
1-23
1 Polar & Nonpolar Molecules
1-24
1 Resonance
• For many molecules and ions, no single Lewis
structure provides a truly accurate
representation
-
O O
CH3 C and CH3 C
O- O
Ethanoate ion
(Acetate ion)
1-25
1 Resonance
• Linus Pauling - 1930s
• many molecules and ions are best described by
writing two or more Lewis structures
• individual Lewis structures are called contributing
structures
• connect individual contributing structures by a double-
headed (resonance) arrow
• the molecule or ion is a hybrid of the various
contributing structures
1-26
1 Resonance
Examples:
-
Nitrite ion O O
(equivalent
N N
contributing
structures) O O-
-
Ethanoate ion O O
(equivalent
CH3 C CH3 C
contributing
structures) O O -
1-27
1 Resonance
• Curved arrow: a symbol used to show the
redistribution of valence electrons
• In using curved arrows, there are only two
allowed types of electron redistribution:
• from a bond to an adjacent atom
• from an atom to an adjacent bond
• Electron pushing by the use of curved arrows is
a survival skill in organic chemistry. Learn it
well!
1-28
1 Resonance
• All acceptable contributing structures must
1. have the same number of valence electrons
2. obey the rules of covalent bonding
• no more than 2 electrons in the valence shell of H
• no more than 8 electrons in valence shell of 2nd
period elements
• 3rd period elements may have up to 12 electrons
in their valence shells
3. differ only in distribution of valence electrons
4. have the same number of paired and unpaired
electrons
1-29
1 Resonance
• Examples of ions and a molecule best
represented as resonance hybrids
carbonate ion CO3 2 -

acetate ion CH3 CO2 -
acetone CH3 COCH3
1-30
1 Valence Bond Model
• a covalent bond is formed
when a portion of an area of overlap
atomic orbital of one atom (the covalent bond)
overlaps a portion of an
atomic orbital of another
atom.
• in forming the covalent
• •
bond in H-H, for example,
there is overlap of the 1s
orbitals of each hydrogen
H H
1-31
1Hybrid Orbitals
• The Problem:
• 2s and 2p atomic orbitals would give bond
angles of approximately 90°
• instead we observe approximately 109.5°,120°,
and 180°
• A Solution
• hybridization of atomic orbitals
• 2nd row elements use sp3, sp2, and sp hybrid
orbitals for bonding
1-32
1 Hybrid Orbitals
• We study three types of hybrid atomic orbitals
sp3 (1 s orbital + 3 p orbitals -> four sp3 orbitals)
sp2 (1 s orbital + 2 p orbitals -> three sp2 orbitals)
sp (1 s orbital + 1 p orbital -> two orbitals)
• Overlap of hybrid atomic orbitals can form two
types of bonds, depending on the geometry of
the overlap
s bonds are formed by “direct” overlap
p bonds are formed by “parallel” overlap
1-33
1 sp3 Hybrid Orbitals
• each sp3 hybrid orbital has
two lobes of unequal size
• the four sp3 hybrid orbitals are
directed toward the corners of
a regular tetrahedron at
angles of 109.5°
1-34
1 sp2 Hybrid Orbitals
• each sp2 hybrid orbital has unhybridized
two lobes of unequal size 2p orbital
• the three sp2 hybrid
orbitals are directed
toward the corners of an
equilateral triangle at
angles of 120°
• the unhybridized 2p orbital
is perpendicular to the sp 2 hybrid
plane of the sp2 hybrid orbitals
orbitals
1-35
1 sp Hybrid Orbitals
• each sp hybrid orbital
has two lobes of unhybridized
unequal size 2p orbitals lie on
the y and z axes
• the two sp hybrid z
orbitals lie in a line at y
an angle of 180°
• the two unhybridized
x
2p orbitals are
perpendicular to each
other and to the line sp hybrid
through the two sp orbitals
hybrid orbitals
1-36
1 Hybrid Orbitals
Hybrid- Types of
ization Bonds to Carbon Example Name
H H
sp3 four sigma bonds H- C- C- H Ethane
H H
H H
sp2 three sigma bonds Ethylene
and one pi bond C C
H H
sp two sigma bonds
H- C C- H Acetylene
and two pi bonds
1-37
1 Functional Groups
• Functional group: an atom or group of atoms
within a molecule that shows a characteristic set
of physical and chemical properties
• Functional groups are important for three
reason; they are
• the units by which we divide organic compounds into
classes
• the sites of characteristic chemical reactions
• the basis for naming organic compounds
1-38
1 Functional Groups
• Hydroxyl (OH) group of alcohols
HH
H- C-C- O- H
H H
An alcohol
(Ethanol)
1-39
1 Functional Groups
• Carbonyl group of aldehydes and ketones
O O
CH3 - C-H CH3 -C- CH3
An aldehyde A ketone
1-40
1 Functional Groups
• Carboxyl group of carboxylic acids
O
CH3 - C-O- H or CH3 COOH or CH3 CO 2 H
Acetic acid
1-41
1 Amines
• Amino group of 1°, 2° and 3° amines
1-42
1
Covalent Bonding
& Shapes of
Molecules
End Chapter 1
1-43

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Number of Relative Energies

Shell Orbitals Contained in That Shell

• if the number assigned to the bonded atom is less than

CH3 - CH3 CO2 - BF 4 -

CH3 CH=CH 2 H2 CO3 HCO3 -

CH3 CHO CH3 CO2 H BF 4 -

carbonate ion CO3 2 -

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