Chemistry: A Molecular Approach, 1st Ed.

Nivaldo Tro

Chapter 9
Chemical
Bonding I:
Lewis Theory
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
2008, Prentice Hall
 Bonding Theories
• explain how and why atoms attach together
• explain why some combinations of atoms are stable
and others are not
 why is water H2O, not HO or H3O
• one of the simplest bonding theories was developed by
G.N. Lewis and is called Lewis Theory
• Lewis Theory emphasizes valence electrons to explain
bonding
• using Lewis Theory, we can draw models – called
Lewis structures – that allow us to predict many
properties of molecules
 aka Electron Dot Structures
 such as molecular shape, size, polarity
Tro, Chemistry: A Molecular Approach 2
 Why Do Atoms Bond?
• processes are spontaneous if they result in a system
with lower potential energy
• chemical bonds form because they lower the potential
energy between the charged particles that compose
atoms
• the potential energy between charged particles is
directly proportional to the product of the charges
• the potential energy between charged particles is
inversely proportional to the distance between the
charges

Tro, Chemistry: A Molecular Approach 3

 Potential Energy Between
Charged Particles
1  q1  q2 
E potential   
4 0  r 
• 0 is a constant
 = 8.85 x 10-12 C2/J∙m
• for charges with the same sign, Epotential is + and the
magnitude gets less positive as the particles get farther
apart
• for charges with the opposite signs, Epotential is  and
the magnitude gets more negative as the particles get
closer together
• remember: the more negative the potential energy, the
more stable the system becomes
Tro, Chemistry: A Molecular Approach 4
 Potential Energy Between
Charged Particles
The repulsion between
like-charged particles
increases as the
particles get closer
together. To bring
them closer requires
the addition of more
energy.

Tro, Chemistry: A Molecular Approach 5

 Potential Energy Between
Charged Particles
The attraction between
opposite-charged
particles increases as
the particles get closer
together. Bringing
them closer lowers the
potential energy of the
system.

Tro, Chemistry: A Molecular Approach 6

 Bonding
• a chemical bond forms when the potential
energy of the bonded atoms is less than the
potential energy of the separate atoms
• have to consider following interactions:
nucleus-to-nucleus repulsion
electron-to-electron repulsion
nucleus-to-electron attraction

Tro, Chemistry: A Molecular Approach 7

 Types of Bonds
Bond
Types of Atoms Type of Bond
Characteristic
metals to electrons
Ionic
nonmetals transferred
nonmetals to electrons
Covalent
nonmetals shared
metal to electrons
Metallic
metal pooled

Tro, Chemistry: A Molecular Approach 8

Types of Bonding

9
 Ionic Bonds
• when metals bond to nonmetals, some electrons
from the metal atoms are transferred to the
nonmetal atoms
metals have low ionization energy, relatively easy to
remove an electron from
nonmetals have high electron affinities, relatively
good to add electrons to

Tro, Chemistry: A Molecular Approach 10

 Covalent Bonds
• nonmetals have relatively high ionization energies, so it
is difficult to remove electrons from them
• when nonmetals bond together, it is better in terms of
potential energy for the atoms to share valence
electrons
 potential energy lowest when the electrons are between the
nuclei
• shared electrons hold the atoms together by attracting
nuclei of both atoms

Tro, Chemistry: A Molecular Approach 11

 Determining the Number of Valence
Electrons in an Atom
• the column number on the Periodic Table will tell you
how many valence electrons a main group atom has
 Transition Elements all have 2 valence electrons; Why?

1A 2A 3A 4A 5A 6A 7A 8A

Li Be B C N O F Ne

1 e-1 2 e-1 3 e-1 4 e-1 5 e-1 6 e-1 7 e-1 8 e-1

Tro, Chemistry: A Molecular Approach 12

 Lewis Symbols of Atoms
• aka electron dot symbols
• use symbol of element to represent nucleus and
inner electrons
• use dots around the symbol to represent valence
electrons
 pair first two electrons for the s orbital
 put one electron on each open side for p electrons
 then pair rest of the p electrons
   
Li          
Be  B   C   N   O   F   Ne 
     
Tro, Chemistry: A Molecular Approach 13
 Lewis Symbols of Ions
• Cations have Lewis symbols without
valence electrons
Lost in the cation formation
• Anions have Lewis symbols with 8 valence
electrons
Electrons gained in the formation of the anion
1
   
Li• Li+1 
 F 

 F  
 
 

  
Tro, Chemistry: A Molecular Approach 14
 What We Know
• the noble gases are the least reactive group
of elements
• the alkali metals are the most reactive
metals and their atoms almost always lose 1
electron when they react
• the halogens are the most reactive group of
nonmetals and in a lot of reactions they gain
1 electron
Tro, Chemistry: A Molecular Approach 15
 Stable Electron Arrangements
And Ion Charge
• Metals form cations by losing
enough electrons to get the
same electron configuration Atom Atom’s Ion Ion’s
as the previous noble gas Electron Electron
• Nonmetals form anions by Config Config
gaining enough electrons to Na [Ne]3s1 Na+1 [Ne]
get the same electron Mg [Ne]3s2 Mg+2 [Ne]
configuration as the next Al [Ne]3s23p1 Al+3 [Ne]
noble gas
O [He]2s22p4 O-2 [Ne]
• The noble gas electron
F [He]2s22p5 F-1 [Ne]
configuration must be very
stable
Tro, Chemistry: A Molecular Approach 16
 Octet Rule
• when atoms bond, they tend to gain, lose, or share electrons to
result in 8 valence electrons
• ns2np6
 noble gas configuration
• many exceptions
 H, Li, Be, B attain an electron configuration like He
 He = 2 valence electrons
 Li loses its one valence electron
 H shares or gains one electron
 though it commonly loses its one electron to become H+
 Be loses 2 electrons to become Be2+
 though it commonly shares its two electrons in covalent bonds, resulting in 4
valence electrons
 B loses 3 electrons to become B3+
 though it commonly shares its three electrons in covalent bonds, resulting in 6
valence electrons
 expanded octets for elements in Period 3 or below
 using empty valence d orbitals

Tro, Chemistry: A Molecular Approach 17

 Lewis Theory
• the basis of Lewis Theory is that there are
certain electron arrangements in the atom that
are more stable
octet rule
• bonding occurs so atoms attain a more stable
electron configuration
more stable = lower potential energy
no attempt to quantify the energy as the calculation
is extremely complex
Tro, Chemistry: A Molecular Approach 18
 Properties of Ionic Compounds
• hard and brittle crystalline solids
Melting an Ionic Solid

all are solids at room temperature

• melting points generally > 300C
• the liquid state conducts electricity
the solid state does not conduct electricity
• many are soluble in water
the solution conducts electricity well

Tro, Chemistry: A Molecular Approach 19

 Conductivity of NaCl

in NaCl(aq), the
in NaCl(s), the ions are
ions are stuck in separated and
position and not allowed to move
allowed to move to the charged
to the charged rods
rods
Tro, Chemistry: A Molecular Approach 20
 Lewis Theory and Ionic Bonding
• Lewis symbols can be used to represent the
transfer of electrons from metal atom to
nonmetal atom, resulting in ions that are
attracted to each other and therefore bond
1
   
Li  + 
F 
Li +  F  
 
 

   

Tro, Chemistry: A Molecular Approach 21

 Predicting Ionic Formulas
Using Lewis Symbols
• electrons are transferred until the metal loses all its
valence electrons and the nonmetal has an octet
• numbers of atoms are adjusted so the electron transfer
comes out even

Li  2
   
 O 
2 Li +  O   Li2O
  

Li     

Tro, Chemistry: A Molecular Approach 22

 Energetics of Ionic Bond Formation
• the ionization energy of the metal is endothermic
 Na(s) → Na+(g) + 1 e ─ DH° = +603 kJ/mol
• the electron affinity of the nonmetal is exothermic
 ½Cl2(g) + 1 e ─ → Cl─(g) DH° = ─ 227 kJ/mol
• generally, the ionization energy of the metal is larger
than the electron affinity of the nonmetal, therefore the
formation of the ionic compound should be
endothermic
• but the heat of formation of most ionic compounds is
exothermic and generally large; Why?
 Na(s) + ½Cl2(g) → NaCl(s) DH°f = -410 kJ/mol
Tro, Chemistry: A Molecular Approach 23
 Ionic Bonds
• electrostatic attraction is nondirectional!!
no direct anion-cation pair
• no ionic molecule
chemical formula is an empirical formula, simply
giving the ratio of ions based on charge balance
• ions arranged in a pattern called a crystal lattice
every cation surrounded by anions; and every anion
surrounded by cations
maximizes attractions between + and - ions

Tro, Chemistry: A Molecular Approach 24

 Lattice Energy
• the lattice energy is the energy released when the
solid crystal forms from separate ions in the gas state
 always exothermic
 hard to measure directly, but can be calculated from
knowledge of other processes
• lattice energy depends directly on size of charges and
inversely on distance between ions

Tro, Chemistry: A Molecular Approach 25

 Born-Haber Cycle
• method for determining the lattice energy of an
ionic substance by using other reactions
use Hess’s Law to add up heats of other processes
• DH°f(salt) = DH°f(metal atoms, g) + DH°f(nonmetal atoms, g)
+ DH°f(cations, g) + DH°f(anions, g) + DH°f(crystal lattice)
 DH°f(crystal lattice) = Lattice Energy
 metal atoms (g)  cations (g), DH°f = ionization energy
don’t forget to add together all the ionization energies to get to the
desired cation
M2+ = 1st IE + 2nd IE
 nonmetal atoms (g)  anions (g), DH°f = electron affinity
Tro, Chemistry: A Molecular Approach 26
 Born-Haber Cycle for NaCl

Tro, Chemistry: A Molecular Approach 27

 Practice - Given the Information Below,
Determine the Lattice Energy of MgCl2

Mg(s)  Mg(g) DH1°f = +147.1 kJ/mol

½ Cl2(g)  Cl(g) DH2°f = +121.3 kJ/mol
Mg(g)  Mg+1(g) DH3°f = +738 kJ/mol
Mg+1(g)  Mg+2(g) DH4°f = +1450 kJ/mol
Cl(g)  Cl-1(g) DH5°f = -349 kJ/mol
Mg(s) + Cl2(g)  MgCl2(s) DH6°f = -641.3 kJ/mol

Tro, Chemistry: A Molecular Approach 28

 Practice - Given the Information Below,
Determine the Lattice Energy of MgCl2
Mg(s)  Mg(g) DH1°f = +147.1 kJ/mol
½ Cl2(g)  Cl(g) DH2°f = +121.3 kJ/mol
Mg(g)  Mg+1(g) DH3°f = +738 kJ/mol
Mg+1(g)  Mg+2(g) DH4°f = +1450 kJ/mol
Cl(g)  Cl-1(g) DH5°f = -349 kJ/mol
Mg(s) + Cl2(g)  MgCl2(s) DH6°f = -641.3 kJ/mol

DH 6f  DH1f  2DH 2f  DH 3f  DH 4f  2DH 5f  DH f latticeenergy


DH f latticeenergy  DH 6 f  DH1f  2DH 2 f  DH 3f  DH 4 f  2DH 5f
     

DH f latticeenergy  (641.3 kJ) - (147.1 kJ)  2(121.3 kJ)  (738 kJ)  (1450 kJ)  2(-349 kJ) 
DH f latticeenergy  2521 kJ

Tro, Chemistry: A Molecular Approach 29

 Trends in Lattice Energy
Ion Size
• the force of attraction between charged
particles is inversely proportional to the
distance between them
• larger ions mean the center of positive charge
(nucleus of the cation) is farther away from
negative charge (electrons of the anion)
larger ion = weaker attraction = smaller lattice
energy

Tro, Chemistry: A Molecular Approach 30

 Lattice Energy vs.
Ion Size
Lattice Energy
Metal Chloride
(kJ/mol)
LiCl -834
NaCl -787
KCl -701
CsCl -657

Tro, Chemistry: A Molecular Approach 31

 Trends in Lattice Energy
Ion Charge
• the force of attraction between
oppositely charged particles is
directly proportional to the product
of the charges Lattice Energy =
-910 kJ/mol
• larger charge means the ions are
more strongly attracted
 larger charge = stronger attraction =
larger lattice energy
• of the two factors, ion charge Lattice Energy =
generally more important -3414 kJ/mol
Tro, Chemistry: A Molecular Approach 32
 Example 9.2 – Order the following ionic
compounds in order of increasing magnitude of
lattice energy.
CaO, KBr, KCl, SrO
First examine the ion charges and Ca2+& O2-, K+ & Br─,
order by product of the charges K+ & Cl─, Sr2+ & O2─
(KBr, KCl) < (CaO, SrO)
Then examine the ion sizes of (KBr, KCl) same cation,
each group and order by radius; Br─ > Cl─ (same Group)
larger < smaller
(CaO, SrO) same anion,
Sr2+ > Ca2+ (same Group)
KBr < KCl < SrO
(CaO,
< SrO)
CaO
Tro, Chemistry: A Molecular Approach 33
 Ionic Bonding
Model vs. Reality
• ionic compounds have high melting points and boiling
points
 MP generally > 300°C
 all ionic compounds are solids at room temperature
• because the attractions between ions are strong,
breaking down the crystal requires a lot of energy
 the stronger the attraction (larger the lattice energy), the
higher the melting point

Tro, Chemistry: A Molecular Approach 34

 Ionic Bonding
Model vs. Reality
• ionic solids are brittle and hard
• the position of the ion in the crystal is critical to
establishing maximum attractive forces –
displacing the ions from their positions results
in like charges close to each other and the
repulsive forces take over
+ +
- -+ +- -+ +- -+ +- -+ +
- -+ + -+ + -+ + -+ + -
- - - -
+ - + - + - + - +
Tro, Chemistry: A Molecular Approach 35
- + - + - + - + -
 Ionic Bonding
Model vs. Reality
• ionic compounds conduct electricity in the liquid state
or when dissolved in water, but not in the solid state
• to conduct electricity, a material must have charged
particles that are able to flow through the material
• in the ionic solid, the charged particles are locked in
position and cannot move around to conduct
• in the liquid state, or when dissolved in water, the ions
have the ability to move through the structure and
therefore conduct electricity
Tro, Chemistry: A Molecular Approach 36
 Covalent Bonding:
Bonding and Lone Pair Electrons
• Covalent bonding results when atoms share pairs
of electrons to achieve an “octet”
• Electrons that are shared by atoms are called
bonding pairs
• Electrons that are not shared by atoms but belong
to a particular atom are called lone pairs
 aka nonbonding pairs

••
•• O •••• ••
Bonding Pairs •• S•• ••O•• Lone Pairs

Tro, Chemistry: A Molecular Approach 37

 Single Covalent Bonds
• two atoms share a pair of electrons
 2 electrons
• one atom may have more than one single bond

•• •• ••
F • • F H• • O •H
••

•
••

•• •• ••
•• •• ••

••
H O H

••
••

••
••

F F
•• •• ••
F F

Tro, Chemistry: A Molecular Approach 38

 Double Covalent Bond
• two atoms sharing two pairs of electrons
4 electrons
•• ••
•O• •O

•
•• ••
O •• O
••
···
·· O
··O ·
Tro, Chemistry: A Molecular Approach 39
 Triple Covalent Bond
• two atoms sharing 3 pairs of electrons
6 electrons
•• ••
•N • •N

•
• •
•
N• N
••
••
··N N ··
Tro, Chemistry: A Molecular Approach 40
 Covalent Bonding
Predictions from Lewis Theory
• Lewis theory allows us to predict the formulas of
molecules
• Lewis theory predicts that some combinations should be
stable, while others should not
 because the stable combinations result in “octets”
• Lewis theory predicts in covalent bonding that the
attractions between atoms are directional
 the shared electrons are most stable between the bonding atoms
 resulting in molecules rather than an array

Tro, Chemistry: A Molecular Approach 41

 Covalent Bonding
Model vs. Reality
• molecular compounds have low melting points and
boiling points
 MP generally < 300°C
 molecular compounds are found in all 3 states at room
temperature
• melting and boiling involve breaking the attractions
between the molecules, but not the bonds between
the atoms
 the covalent bonds are strong
 the attractions between the molecules are generally weak
 the polarity of the covalent bonds influences the strength of
the intermolecular attractions
Tro, Chemistry: A Molecular Approach 42
 Intermolecular Attractions vs. Bonding

Tro, Chemistry: A Molecular Approach 43

 Ionic Bonding
Model vs. Reality
• some molecular solids are brittle and hard, but
many are soft and waxy
• the kind and strength of the intermolecular
attractions varies based on many factors
• the covalent bonds are not broken, however, the
polarity of the bonds has influence on these
attractive forces

Tro, Chemistry: A Molecular Approach 44

 Ionic Bonding
Model vs. Reality
• molecular compounds do not conduct electricity in the
liquid state
• molecular acids conduct electricity when dissolved in
water, but not in the solid state
• in molecular solids, there are no charged particles
around to allow the material to conduct
• when dissolved in water, molecular acids are ionized,
and have the ability to move through the structure and
therefore conduct electricity
Tro, Chemistry: A Molecular Approach 45
 Bond Polarity
• covalent bonding between unlike atoms results in
unequal sharing of the electrons
one atom pulls the electrons in the bond closer to its side
one end of the bond has larger electron density than the
other
• the result is a polar covalent bond
bond polarity
the end with the larger electron density gets a partial
negative charge
the end that is electron deficient gets a partial positive
charge
Tro, Chemistry: A Molecular Approach 46
 HF


EN 2.1 H F  EN 4.0



d H •• F d

Tro, Chemistry: A Molecular Approach 47

 Electronegativity
• measure of the pull an atom has on bonding
electrons
• increases across period (left to right) and
• decreases down group (top to bottom)
fluorine is the most electronegative element
francium is the least electronegative element
• the larger the difference in electronegativity,
the more polar the bond
negative end toward more electronegative atom
Tro, Chemistry: A Molecular Approach 48
 Electronegativity Scale

Tro, Chemistry: A Molecular Approach 49

 Electronegativity and Bond Polarity
• If difference in electronegativity between bonded atoms
is 0, the bond is pure covalent
 equal sharing
• If difference in electronegativity between bonded atoms
is 0.1 to 0.4, the bond is nonpolar covalent
• If difference in electronegativity between bonded atoms
0.5 to 1.9, the bond is polar covalent
• If difference in electronegativity between bonded atoms
larger than or equal to 2.0, the bond is ionic
Percent Ionic Character
4% 51% “100%”

0 0.4 2.0 4.0

Electronegativity Difference 50
 Bond Polarity

ENCl = 3.0 ENCl = 3.0 ENCl = 3.0

3.0 - 3.0 = 0 ENH = 2.1 ENNa = 1.0
Pure Covalent 3.0 – 2.1 = 0.9 3.0 – 0.9 = 2.1
Polar Covalent Ionic

Tro, Chemistry: A Molecular Approach 51

Tro, Chemistry: A Molecular Approach 52
 Bond Dipole Moments
• the dipole moment is a quantitative way of describing the
polarity of a bond
 a dipole is a material with positively and negatively charged ends
 measured
• dipole moment, m, is a measure of bond polarity
 it is directly proportional to the size of the partial charges and
directly proportional to the distance between them
 m = (q)(r)
 not Coulomb’s Law
 measured in Debyes, D
• the percent ionic character is the percentage of a bond’s
measured dipole moment to what it would be if full ions
Tro, Chemistry: A Molecular Approach 53
 Dipole Moments

Tro, Chemistry: A Molecular Approach 54

 Water – a Polar Molecule

stream of stream of
water hexane
attracted not
to a attracted
charged to a
glass rod charged
glass rod

Tro, Chemistry: A Molecular Approach 55

 Example 9.3(c) - Determine whether an N-O
bond is ionic, covalent, or polar covalent.
• Determine the electronegativity of each element
N = 3.0; O = 3.5
• Subtract the electronegativities, large minus small
(3.5) - (3.0) = 0.5
• If the difference is 2.0 or larger, then the bond is
ionic; otherwise it’s covalent
difference (0.5) is less than 2.0, therefore covalent
• If the difference is 0.5 to 1.9, then the bond is
polar covalent; otherwise it’s covalent
difference (0.5) is 0.5 to 1.9, therefore polar covalent
Tro, Chemistry: A Molecular Approach 56
 Lewis Structures
of Molecules
• shows pattern of valence electron distribution in
the molecule
• useful for understanding the bonding in many
compounds
• allows us to predict shapes of molecules
• allows us to predict properties of molecules and
how they will interact together

Tro, Chemistry: A Molecular Approach 57

 Lewis Structures
• use common bonding patterns
 C = 4 bonds & 0 lone pairs, N = 3 bonds & 1 lone pair,
O= 2 bonds & 2 lone pairs, H and halogen = 1 bond, Be
= 2 bonds & 0 lone pairs, B = 3 bonds & 0 lone pairs
 often Lewis structures with line bonds have the lone
pairs left off
 their presence is assumed from common bonding patterns
• structures which result in bonding patterns
different from common have formal charges

B C N O F
Tro, Chemistry: A Molecular Approach 58
 Writing Lewis Structures of Molecules
HNO3 O
1) Write skeletal structure
 H always terminal
 in oxyacid, H outside attached to O’s
H O N O
 make least electronegative atom central
 N is central

2) Count valence electrons N=5

 sum the valence electrons for each H=1
atom
 add 1 electron for each − charge
O3 = 3∙6 = 18
 subtract 1 electron for each + charge Total = 24 e-

Tro, Chemistry: A Molecular Approach 59

 Writing Lewis Structures of Molecules
HNO3
3) Attach central atom to the surrounding atoms with
pairs of electrons and subtract from the total

O Electrons
Start 24
 Used 8
H — O — N — O Left 16

Tro, Chemistry: A Molecular Approach 60

Writing Lewis Structures of Molecules
HNO3

4) Complete octets, outside-in : O :
 H is already complete with 2
 
 1 bond H — O — N — O :
 

and re-count electrons

N=5 Electrons Electrons
H=1 Start 24 Start 16
O3 = 3∙6 = 18 Used 8 Used 16
Total = 24 e- Left 16 Left 0
Tro, Chemistry: A Molecular Approach 61
 Writing Lewis Structures of Molecules
HNO3
5) If all octets complete, give extra
electrons to central atom.
 elements with d orbitals can have
more than 8 electrons
 Period 3 and below


6) If central atom does not have O : :

 | 
O:
octet, bring in electrons from
outside atoms to share H — O — N

 follow common bonding patterns
if possible

Tro, Chemistry: A Molecular Approach 62

 Practice - Lewis Structures
• CO2 • H3PO4

• SeOF2 • SO3-2

• NO2-1 • P2H4

Tro, Chemistry: A Molecular Approach 63

 Practice - Lewis Structures
••
•O•
• CO2 16 e- • H3PO4 ••
• •
••
H O P O H
:O::C::O: 32 e- •• ••
•O H
•
••

• SeOF2 ••
•O•
• SO3-2 ••
•O•
• • • •
26 e- • •• •• 26 e- •• ••
•O O ••
•F Se F •• • S
•• •• •• •• •• ••
• NO2-1 • P2H4
H H
•• •• ••
18 e- •O N O •• 14 e-
•
•• H P P H
•• ••
Tro, Chemistry: A Molecular Approach 64
 Formal Charge
• during bonding, atoms may wind up with more
or less electrons in order to fulfill octets - this
results in atoms having a formal charge
FC = valence e- - nonbonding e- - ½ bonding e-
left O FC = 6 - 4 - ½ (4) = 0 •• •••• • •• •
O •• S • O •
S FC = 6 - 2 - ½ (6) = +1 •• ••
right O FC = 6 - 6 - ½ (2) = -1
• sum of all the formal charges in a molecule = 0
 in an ion, total equals the charge
Tro, Chemistry: A Molecular Approach 65
 Writing Lewis Formulas of
Molecules (cont’d)
7) Assign formal charges to the atoms
a) formal charge = valence e- - lone pair e- - ½ bonding e-
b) follow the common bonding patterns


   H O 
0 +1  -1  | || 
 O  S O
    H  C  C  O  H
 | 

H all 0
Tro, Chemistry: A Molecular Approach 66
 Common Bonding Patterns
B C N O F

+ + + +
C N O F

- - - - -
B C N O F

Tro, Chemistry: A Molecular Approach 67

 Practice - Assign Formal Charges
••
•O•
• •
• CO2 • H3PO4 •• ••
H O P O H
•• ••
•O H
•
••
• SeOF2 ••
•O• • SO3-2 ••
•O•
• • • •
•• •• •• ••
•F •O O ••
• Se F •• •
••
S
••
•• •• •• ••
• NO2-1 • P2H4
H H
•• •• ••
•O N O ••
• H P P H
••
•• ••
Tro, Chemistry: A Molecular Approach 68
 Practice - Assign Formal Charges
•• -1
•O•
• •
• CO2 • H3PO4 •• ••
all 0 P = +1 H O
••
P O
••
H
rest 0 •O H
•
••
• SeOF2 •• -1
•O• • SO3-2 •• -1
•O•
• • • •
Se = +1 •• •• S = +1 ••-1 •• -1
•F •O O ••
• Se F •• •
••
S
••
•• •• •• ••
• NO2-1 • P2H4
H H
•• •• •• -1
•O N O •• all 0
• H P P H
••
•• ••
Tro, Chemistry: A Molecular Approach 69
 Resonance
• when there is more than one Lewis structure for a
molecule that differ only in the position of the
electrons, they are called resonance structures
• the actual molecule is a combination of the
resonance forms – a resonance hybrid
it does not resonate between the two forms,
though we often draw it that way
• look for multiple bonds or lone pairs
••
•• O •• •• •• •• ••
••S •• ••
•• S •• O
••
•• •• O
•• •• O ••
Tro, Chemistry: A Molecular Approach 70
 Resonance

Tro, Chemistry: A Molecular Approach 71

 Ozone Layer

Tro, Chemistry: A Molecular Approach 72

 Rules of Resonance Structures
• Resonance structures must have the same connectivity
 only electron positions can change
• Resonance structures must have the same number of
electrons
• Second row elements have a maximum of 8 electrons
 bonding and nonbonding
 third row can have expanded octet
• Formal charges must total same
• Better structures have fewer formal charges
• Better structures have smaller formal charges
• Better structures have − formal charge on more
electronegative atom
Tro, Chemistry: A Molecular Approach 73
 Drawing Resonance Structures
1. draw first Lewis structure that
maximizes octets
2. assign formal charges
·· -1
··O ··
3. move electron pairs from atoms
with (-) formal charge toward
·· O N
··-1
O ··
atoms with (+) formal charge
4. if (+) fc atom 2nd row, only move ·· +1
··
in electrons if you can move out
electron pairs from multiple ··-1
·· O ··
bond
5. if (+) fc atom 3rd row or below,
keep bringing in electron pairs to
-1
··
··O N
+1
··
O
reduce the formal charge, even if
get expanded octet.
·· ··
Tro, Chemistry: A Molecular Approach 74
 Exceptions to the Octet Rule
• expanded octets
elements with empty d orbitals can have more
than 8 electrons
• odd number electron species e.g., NO
will have 1 unpaired electron
free-radical
very reactive
• incomplete octets
B, Al
Tro, Chemistry: A Molecular Approach 75
 Drawing Resonance Structures
1. draw first Lewis structure that
maximizes octets ··-1
··O ··
2. assign formal charges
3. move electron pairs from atoms H
··
O S
+2 ··
O H
with (-) formal charge toward ·· ··
atoms with (+) formal charge ·
· O ··
-1 ··
4. if (+) fc atom 2nd row, only move
in electrons if you can move out
electron pairs from multiple bond
5. if (+) fc atom 3rd row or below,
·· 0
O ··
keep bringing in electron pairs to
reduce the formal charge, even if H
··
O S
0 ··
O H
get expanded octet. ·· ··
·· O 0
Tro, Chemistry: A Molecular Approach
·· 76
 Practice - Identify Structures with Better or
Equal Resonance Forms and Draw Them ••
• O • -1
• •
• CO2 • H3PO4 •• ••
all 0 P = +1 H O
••
P O
••
H
•O H
•
••
• SeOF2 •• -1
•O• • SO3-2 •• -1
•O•
• • • •
Se = +1 •• •• S = +1 ••-1 •• -1
•F •O O ••
• Se F •• •
••
S
••
•• •• •• ••
• NO2-1 • P2H4
H H
•• •• •• -1
•O N O •• all 0
• H P P H
••
•• ••
Tro, Chemistry: A Molecular Approach 77
 Practice - Identify Structures with Better or
Equal Resonance Forms and Draw Them
• CO2 -1 • ••••
H3PO4 • •• all 0
•O• •O
•• •• •• ••
none H O P O H H O P O H
•• +1 •• •• ••
•O H •O H
• •
•• ••

• SeOF2 • SO3-2 ••
•O•
••
•O•
••
•O•
•• ••
• • • • • •
• O • -1 •O •O
•• ••
O• •O
•• ••
O• •O
•• ••
O ••
• • all 0 • • S
•• •• •
•
••
S
•• •• • •
••
S
••
•• •• •• ••
•F Se F •• •F
• • Se F •• S=0
•• •• •• •• •• ••
+1 •O•
• • in all
• NO2-1 • P2H4 •O
•
••
••
S
••
••
O•
•• •
res. forms

•• •• •• -1 -1
•• •• •• H H
•O N O •• •O N O ••
• •
•• ••
Tro, Chemistry: A Molecular Approach H P P H none 78
•• ••
 Bond Energies
• chemical reactions involve breaking bonds in reactant
molecules and making new bond to create the products
• the DH°reaction can be calculated by comparing the cost
of breaking old bonds to the profit from making new
bonds
• the amount of energy it takes to break one mole of a
bond in a compound is called the bond energy
 in the gas state
 homolytically – each atom gets ½ bonding electrons

Tro, Chemistry: A Molecular Approach 79

 Trends in Bond Energies
• the more electrons two atoms share, the stronger
the covalent bond
C≡C (837 kJ) > C=C (611 kJ) > C−C (347 kJ)
C≡N (891 kJ) > C=N (615 kJ) > C−N (305 kJ)
• the shorter the covalent bond, the stronger the
bond
Br−F (237 kJ) > Br−Cl (218 kJ) > Br−Br (193 kJ)
bonds get weaker down the column

Tro, Chemistry: A Molecular Approach 80

Using Bond Energies to Estimate DH°rxn
• the actual bond energy depends on the surrounding
atoms and other factors
• we often use average bond energies to estimate the
DHrxn
 works best when all reactants and products in gas state
• bond breaking is endothermic, DH(breaking) = +
• bond making is exothermic, DH(making) = −
DHrxn = ∑ (DH(bonds broken)) + ∑ (DH(bonds formed))

Tro, Chemistry: A Molecular Approach 81

82
Estimate the Enthalpy of the Following Reaction

H H + O O H O O H

83
Estimate the Enthalpy of the Following Reaction

H2(g) + O2(g)  H2O2(g)

reaction involves breaking 1mol H-H and 1 mol O=O
and making 2 mol H-O and 1 mol O-O
bonds broken (energy cost)
(+436 kJ) + (+498 kJ) = +934 kJ
bonds made (energy release)
2(464 kJ) + (142 kJ) = -1070
DHrxn = (+934 kJ) + (-1070. kJ) = -136 kJ
(Appendix DH°f = -136.3 kJ/mol)

Tro, Chemistry: A Molecular Approach 84

 Bond Lengths
• the distance between the nuclei of
bonded atoms is called the bond
length
• because the actual bond length
depends on the other atoms around
the bond we often use the average
bond length
averaged for similar bonds from
many compounds
Tro, Chemistry: A Molecular Approach 85
 Trends in Bond Lengths
• the more electrons two atoms share, the shorter the
covalent bond
 C≡C (120 pm) < C=C (134 pm) < C−C (154 pm)
 C≡N (116 pm) < C=N (128 pm) < C−N (147 pm)
• decreases from left to right across period
 C−C (154 pm) > C−N (147 pm) > C−O (143 pm)
• increases down the column
 F−F (144 pm) > Cl−Cl (198 pm) > Br−Br (228 pm)
• in general, as bonds get longer, they also get weaker
Tro, Chemistry: A Molecular Approach 86
 Bond Lengths

Tro, Chemistry: A Molecular Approach 87

 Metallic Bonds
• low ionization energy of metals allows them to
lose electrons easily
• the simplest theory of metallic bonding involves
the metals atoms releasing their valence electrons
to be shared by all to atoms/ions in the metal
an organization of metal cation islands in a sea of
electrons
electrons delocalized throughout the metal structure
• bonding results from attraction of cation for the
delocalized electrons
Tro, Chemistry: A Molecular Approach 88
 Metallic Bonding

Tro, Chemistry: A Molecular Approach 89

 Metallic Bonding
Model vs. Reality
• metallic solids conduct electricity
• because the free electrons are mobile, it
allows the electrons to move through the
metallic crystal and conduct electricity
• as temperature increases, electrical
conductivity decreases
• heating causes the metal ions to vibrate
faster, making it harder for electrons to make
their way through the crystal
Tro, Chemistry: A Molecular Approach 90
 Metallic Bonding
Model vs. Reality
• metallic solids conduct heat
• the movement of the small, light electrons
through the solid can transfer kinetic energy
quicker than larger particles
• metallic solids reflect light
• the mobile electrons on the surface absorb
the outside light and then emit it at the same
frequency
Tro, Chemistry: A Molecular Approach 91
 Metallic Bonding
Model vs. Reality
• metallic solids are malleable and ductile
• because the free electrons are mobile, the
direction of the attractive force between the
metal cation and free electrons is adjustable
• this allows the position of the metal cation
islands to move around in the sea of
electrons without breaking the attractions
and the crystal structure

Tro, Chemistry: A Molecular Approach 92

 Metallic Bonding
Model vs. Reality
• metals generally have high melting points and boiling
points
 all but Hg are solids at room temperature
• the attractions of the metal cations for the free electrons
is strong and hard to overcome
• melting points generally increase to right across period
• the charge on the metal cation increases across the
period, causing stronger attractions
• melting points generally decrease down column
• the cations get larger down the column, resulting in a
larger distance from the nucleus to the free electrons
Tro, Chemistry: A Molecular Approach 93