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Chemistry
William H. Brown
Christopher S. Foote
Brent L. Iverson
1-1
Covalent
Bonding &
Shapes of
Molecules
Chapter 1
1-2
Organic Chemistry
The study of the compounds of carbon
Over 10 million compounds have been
identified
• about 1000 new ones are 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
Schematic View of an Atom
• a small dense
nucleus, diameter 10-
14 - 10-15 m, which
contains positively
charged protons and
most of the mass of
the atom
• an extranuclear
space, diameter 10-10
m, which contains
negatively charged
electrons
1-4
Electron Configuration of Atoms
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
Electron Configuration of Atoms
Shells are divided into subshells called
orbitals, which are designated by the
letters s, p, d, f,........
• s (one per shell)
• p (set of three per shell 2 and higher)
• d (set of five per shell 3 and higher) .....
1-6
Electron Configuration of Atoms
Aufbau Principle:
• orbitals fill in order of increasing energy from
lowest energy to highest energy
Pauli Exclusion Principle:
• only two electrons can occupy an orbital and
their spins must be paired
Hund’s Rule:
• when orbitals of equal energy are available but
there are not enough electrons to fill all of
them, one electron is added to each orbital
before a second electron is added to any one of
them
1-7
Electron Configuration of Atoms
The pairing of electron spins
1-8
Electron Configuration of Atoms
Table 1.3 The Ground-State Electron
Configuration of Elements 1-18
1-9
Lewis Dot Structures
Gilbert N. Lewis
Valence shell:
• the outermost occupied electron shell of an
atom
Valence electrons:
• electrons in the valence shell of an atom; these
electrons are used to form chemical bonds and
in chemical reactions
Lewis dot structure:
• the symbol of an element represents the
nucleus and all inner shell electrons
• dots represent valence electrons
1-10
Lewis Dot Structures
Table 1.4 Lewis Dot Structures for Elements 1-18
1A 2A 3A 4A 5A 6A 7A 8A
H. He :
. . . . . :
Li . Be : B: C : .N : :O. : :F
: : :Ne
: :
. . . . . :
Na. Mg : Al : Si : .P: :S. : :Cl
: : :Ar
: :
1-11
Lewis Model of Bonding
Atoms bond together so that each atom
acquires an electron configuration the same
as that of the noble gas nearest it in atomic
number
• an atom that gains electrons becomes an anion
• an atom that loses electrons becomes a cation
• the attraction of anions and cations leads to the
formation of ionic solids
• an atom may share electrons with one or more
atoms to complete its valence shell; a chemical
bond formed by sharing electrons is called a
covalent bond
• bonds may be partially ionic or partially covalent;
these bonds are called polar covalent bonds
1-12
Electronegativity
Electronegativity:
• a measure of an atom’s attraction for the
electrons it shares with another atom in a
chemical bond
Pauling scale
• generally increases left to right in a row
• generally increases bottom to top in a column
1-13
Formation of Ions
A rough guideline:
• ions will form if the difference in
electronegativity between interacting atoms is
1.9 or greater
• example: sodium (EN 0.9) and fluorine (EN 4.0)
• we use a single-headed (barbed) curved arrow
to show the transfer of one
•• ••
+
electron
-
from Na to
• • ••
••
Na + F Na F
F •• ••
• in
Na(1s2 forming Na2+2s
2s 22p63s1 ) + F(1s F-2,2pthe
5
)
single s 2electron
Na+3(1s from
2s22p6) + F-(1s2 Na
2s2 2p6 )
is transferred to the partially filled valence
shell of F
1-14
Covalent Bonds
The simplest covalent bond is that in H2
• the single electrons from each atom combine to
form an electron pair
HΔ + •H H-H ΔH 0 = -435 kJ (-104 kcal)/m ol
1-15
Polar and Nonpolar Covalent
Bonds
Although all covalent bonds involve
sharing of electrons, they differ widely in
the degree of sharing
We divide covalent bonds into
• nonpolar covalent bonds
• polar covalent 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 Ions form
1-16
Polar and Nonpolar Covalent
Bonds
• an example of a polar covalent bond is that of
H-Cl
• the difference in electronegativity between Cl
and H is 3.0 - 2.1 = 0.9
• we show polarity by using the symbols + and
-, or by using an arrow with the arrowhead
pointing toward the negative end and a plus
sign on the tail of the arrow at the positive end
Δ+ δ-
H Cl H Cl
1-17
Polar Covalent Bonds
Bond dipole moment (m ):
• a measure of the polarity of a covalent bond
• the product of the charge on either atom of a
polar bond times the distance between the
nuclei
• Table 1.7 shows average bond dipole moments
of selected covalent bonds
Bond Bond Bond
Dipole Dipole Dipole
Bond (D) Bond (D) Bond (D)
1-21
Formal Charge
Example: Draw Lewis structures, and show which
atom in each bears the formal charge
- - 2-
(a) NH2 (b) HCO3 (c) CO3
+ - -
(d) CH3 NH3 (e) HCOO (f) CH3COO
1-22
Exceptions to the Octet Rule
Molecules containing atoms of Group 3A
elements, particularly boron and aluminum
: 6 electrons in the
:F:
:
valence shells of boron :Cl :
and aluminum
: :
: :
:F B :Cl Al
:F : :Cl :
:
:
Boron trifluoride Aluminum chloride
1-23
Exceptions to the Octet Rule
Atoms of third-period elements have 3d
orbitals and may expand their valence
shells to contain more than 8 electrons
• phosphorus may have up : to 10
: :Cl: : : O:
: : Cl : :
: Cl
: :
CH3 -P- CH3 : P : H- :O-P- O-H
:
CH3 : Cl
: Cl
: : O-H
:
Trimethyl- Phosphorus Phosphoric
phosphine pentachloride acid
1-24
Exceptions to the Octet Rule
• sulfur, another third-period element, forms
compounds in which its valence shell contains
8, 10, or 12 electrons
: O: : O:
: : :
H-S-H
: CH3 -S-CH
: 3 H-O-S-O-H
: :
: O:
1-25
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
1. the units by which we divide organic
compounds into classes
2. the sites of characteristic chemical reactions
3. the basis for naming organic compounds
1-26
Alcohols
contain an -OH (hydroxyl)
hydroxyl group
: HH
-C-O-H
: H-C-C-O-H
HH
Functional Ethanol
group (an alcohol)
1-27
Alcohols
• alcohols are classified as primary (1°),
secondary (2°), or tertiary (3°) depending on the
number of carbon atoms bonded to the carbon
bearing theCH
-OH
3 group H CH3
CH3 -C-OH CH3 -C-OH CH3 -C-OH
CH3 CH3 CH3
A 1° alcohol A 2° alcohol A 3° alcohol
1-28
Alcohols
• there are two alcohols with molecular formula
C3H8O
HHH
H-C-C-C-O-H or CH3 CH2CH2 OH
H HH a 1° alcohol
H
HOH OH
H C-C-C-H or CH3CHCH3
HH H a 2° alcohol
1-29
Amines
group an sp3-hybridized
contain an amino group;
nitrogen bonded to one, two, or three
carbon atoms
• an amine may by 1°, 2°, or 3°
:
:
:
CH3 N H CH3 N H CH3 N CH3
H CH3 CH3
Methylamine Dimethylamine Trimethylamine
(a 1° amine) (a 2° amine) (a 3° amine)
1-30
Aldehydes and Ketones
contain a carbonyl (C=O) group
O O O O
C H CH3-C-H C CH3 -C-CH3
Functional Acetaldehyde Functional Acetone
group (an aldehyde) group (a ketone)
1-31
Carboxylic Acids
contain a carboxyl (-COOH) group
O :O::
C O H CH3 -C-O-H
: or CH3COOH or CH3 CO2 H
Functional Acetic acid
group (a carboxylic acid)
1-32
Carboxylic Esters
Ester: a derivative of a carboxylic acid in
which the carboxyl hydrogen is replaced
by a carbon group
O : O: :
C O CH3 -C-O-CH
: 2 -CH3
1-33
Carboxylic Amide
Carboxylic amide,
amide commonly referred to as
an amide:
amide a derivative of a carboxylic acid
in which the -OH of the -COOH group is
replaced by an amine
O O
C N CH3 -C-N-H
H
Functional Acetamide
group (a 1° amide)
1-34
VSEPR
Based on the twin concepts that
• atoms are surrounded by regions of electron
density
• regions of electron density repel each other
H
:
4 regions of e- density
C N O
(tetrahedral, 109.5°) H H H
H H H H H
H H H : H H
3 regions of e- density
(trigonal planar, 120°) C C C :
O C N
:
H H H H
: :
2 regions of e- density
:O C O
: H C C H H C N
(linear, 180°)
1-35
VSEPR Model
Example: predict all bond angles for these
molecules and ions
(a) NH4 + (b) CH3 NH2 (d) CH3 OH
(e) CH3 CH=CH2 (f) H2 CO3 (g) HCO3 -
(h) CH3 CHO (i) CH3COOH (j) BF4 -
1-36
Polar and Nonpolar Molecules
To determine if a molecule is polar, we
need to determine
• if the molecule has polar bonds
• the arrangement of these bonds in space
Molecular dipole moment (m ): the vector
sum of the individual bond dipole moments
in a molecule
• reported in debyes (D)
1-37
Polar and Nonpolar Molecules
these molecules have polar bonds, but
each has a zero dipole moment
F Cl
O C O B F C
F Cl Cl
Cl
Carbon dioxide Boron trifluorie Carbon tetrachlorie
Δ=0D Δ=0D Δ=0D
1-38
Polar and Nonpolar Molecules
these molecules have polar bonds and are
polar molecules
irection O N irection
of ip ole of ip ole
H H H H
m om ent m om ent
H
Water Am m onia
Δ = 1.85D Δ = 1.47D
1-39
Polar and Nonpolar Molecules
• formaldehyde has polar bonds and is a polar
molecule
irection O
of ip ole C
m om ent H H
Formaldehyde
Δ = 2.33 D
1-40
Resonance
For many molecules and ions, no single
Lewis structure provides a truly accurate
representation
-
O O
H3 C C and H3 C C
O O
-
Ethanoate ion
(acetate ion)
1-41
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
double-headed (resonance) arrows
• the molecule or ion is a hybrid of the various
contributing structures
1-42
Resonance
Examples: equivalent contributing structures
: : : :
:O:- O: : O: -
O:
:N :N CH3 C CH3 C
: :
O :O
: :- : :
O :O
: :-
Nitrite ion Acetate ion
(equivalent contributing (equivalent contributing
structures) structures)
1-43
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 is a survival skill in
organic chemistry
• learn it well!
1-44
Resonance
All 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 the valence shell of
a 2nd period element
• 3rd period elements, such as P and S, may have
up to 12 electrons in their valence shells
3. differ only in distribution of valence electrons;
the position of all nuclei must be the same
4. have the same number of paired and unpaired
electrons
1-45
Resonance
The carbonate ion, for example
• a hybrid of three equivalent contributing
structures
• the negative charge is distributed equally
among the three oxygens
1-46
Resonance
Preference 1: filled valence shells
• structures in which all atoms have filled
valence shells contribute more than those with
one or more unfilled valence shells
+ •• +
CH3 O C H CH3 O C H
•• ••
H H
Greater contribution; Lesser contribution;
both carbon and oxygen havecarbon has only 6 electrons
complete valence shells in its valence shell
1-47
Resonance
Preference 2: maximum number of
covalent bonds
• structures with a greater number of covalent
bonds contribute more than those with fewer
covalent bonds
+ •• +
CH3 ••
O C H CH3 ••
O C H
H H
Greater contribution Lesser contribution
(8 covalent bonds) (7 covalent bonds)
1-48
Resonance
Preference 3: least separation of unlike
charge
• structures with separation of unlike charges
:
contributeO:less than those with
:O: - no charge
:
separation
CH3 -C-CH3 CH3 -C-CH3
Greater contributionLesser contribution
(no separation of (separation of unlike
unlike charges) charges)
1-49
Resonance
Preference 4: negative charge on the more
electronegative atom
• structures that carry a negative charge on the
more electronegative atom contribute more
than those with the negative charge on the less
electronegative atom
O O O
(1) C (2)
C C
H3 C CH3 H3 C CH3 H3 C CH3
(a) (b) (c)
Lesser Greater Should not
contribution contribution be drawn
1-50
Quantum or Wave Mechanics
Albert Einstein: E = hn (energy is quantized)
• light has particle properties
Louis deBroglie: wave/particle duality
h
Δ = mν
Erwin Schrödinger: wave equation
• wave function, : a solution to a set of equations
that depicts the energy of an electron in an atom
• each wave function is associated with a unique
set of quantum numbers
• each wave function occupies three-dimensional
space and is called an orbital
• 2 is the probability of finding an electron at a
given point in space
1-51
Shapes of 1s and 2s Orbitals
Probability distribution ( 2) for 1s and 2s
orbitals showing an arbitrary boundary
surface containing about 95% of the
electron density
1-52
Shapes of a Set of 2p Atomic
Orbitals
Three-dimensional shapes of 2p atomic
orbitals
1-53
Molecular Orbital Theory
Electrons in atoms exist in atomic orbitals
Electrons in molecules exist in molecular
orbitals (MOs)
Using the Schrödinger equation, we can
calculate the shapes and energies of MOs
1-54
Molecular Orbital Theory
Rules:
• combination of n atomic orbitals
(mathematically adding and subtracting wave
functions) gives n MOs (new wave functions)
• MOs are arranged in order of increasing energy
• MO filling is governed by the same rules as for
atomic orbitals:
• Aufbau principle: fill beginning with LUMO
• Pauli exclusion principle: no more than 2e- in
a MO
• Hund’s rule: when two or more MOs of
equivalent energy are available, add 1e- to
each before filling any one of them with 2e-
1-55
Molecular Orbital Theory
Terminology
• ground state = lowest energy state
• excited state = NOT lowest energy state
• = sigma bonding MO
• * = sigma antibonding MO
• p = pi bonding MO
• p* = pi antibonding MO
• HOMO = highest occupied MO
• LUMO = lowest unoccupied MO
1-56
Molecular Orbital Theory
Sigma 1s bonding and antibonding MOs
1-57
Molecular Orbital Theory
• MO energy diagram for H2: (a) ground state and
(b) lowest excited state
1-58
Molecular Orbitals
• computed sigma bonding and antibonding MOs
for H2
1-59
Molecular Orbitals
pi bonding and antibonding MOs
1-60
Molecular Orbitals
• computed pi bonding and antibonding MOs for
ethylene
1-61
Molecular Orbitals
• computed pi bonding and antibonding orbitals
for formaldehyde
1-62
Hybrid Orbitals
The Problem:
• bonding by 2s and 2p atomic orbitals would
give bond angles of approximately 90°
• instead we observe bond angles of
approximately 109.5°, 120°, and 180°
A Solution
• hybridization of atomic orbitals
• 2nd row elements use sp3, sp2, and sp hybrid
orbitals for bonding
1-63
Hybrid Orbitals
Hybridization of orbitals (L. Pauling)
• the combination of two or more atomic orbitals
forms a new set of atomic orbitals, called hybrid
orbitals
We deal with three types of hybrid orbitals
sp3 (one s orbital + three p orbitals)
sp2 (one s orbital + two p orbitals)
sp (one s orbital + one p orbital)
Overlap of hybrid orbitals can form two types
of bonds depending on the geometry of
overlap
bonds are formed by “direct” overlap
p bonds are formed by “parallel” overlap
1-64
sp3 Hybrid Orbitals
• each sp3 hybrid
orbital has two lobes
of unequal size
• the sign of the wave
function is positive
in one lobe, negative
in the other, and zero
at the nucleus
• the four sp3 hybrid
orbitals are directed
toward the corners
of a regular
tetrahedron at
angles of 109.5°
1-65
sp3 Hybrid Orbitals
• orbital overlap pictures of methane, ammonia,
and water
1-66
sp2 Hybrid Orbitals
• the axes of the three sp2 hybrid orbitals lie in a
plane and are directed toward the corners of an
equilateral triangle
• the unhybridized 2p orbital lies perpendicular to
the plane of the three hybrid orbitals
1-67
Bonding in Ethylene
1-68
Bonding in Formaldehyde
1-69
sp Hybrid Orbitals
• two lobes of unequal size at an angle of 180°
• the unhybridized 2p orbitals are perpendicular
to each other and to the line created by the
axes of the two sp hybrid orbitals
1-70
Bonding in Acetylene, C2H2
1-71
Hybrid Orbitals
Groups Orbital Predicted Types of
Bonded Hybrid- Bond Bonds
to Carbon ization Angles to Carbon Example Name
HH
4 sp3 109.5° 4 sigma bonds H-C-C-H Ethane
HH
H H
sp 2
120° 3 sigma bonds
2 C C Ethylene
and 1 pi bond
H H
1-72
Bond Lengths and Bond Strengths
1-73
Covalent
Bonds &
Shapes of
Molecules
End Chapter 1
1-74