Brown Et Al - Chapter 8

Chapter 8
Basic Concepts of Chemical

Bonding
Chemical Bonds, Lewis Symbols, and

the Octet Rule
Chemical bond: attractive force holding two or more
atoms together.
Covalent bond results from sharing electrons between
the atoms. Usually found between nonmetals.
Ionic bond results from the transfer of electrons from a
metal to a nonmetal.
Metallic bond: attractive force holding pure metals
together.
Lewis Symbols
As a pictorial understanding of where the electrons are in
an atom, we represent the electrons as dots around the
symbol for the element.
The number of electrons available for bonding are
indicated by unpaired dots.
These symbols are called Lewis symbols.
We generally place the electrons one four sides of a
square around the element symbol.
Lewis Symbols
The Octet Rule

All noble gases except He has an s2p6 configuration.
Octet rule: atoms tend to gain, lose, or share electrons
until they are surrounded by 8 valence electrons (4
electron pairs).
Caution: there are many exceptions to the octet rule.
Ionic Bonding
The reaction is violently exothermic.
We infer that the NaCl is more stable than its
constituent elements. Why?
Na has lost an electron to become Na+ and chlorine has
gained the electron to become Cl. Note: Na+ has an Ne
electron configuration and Cl has an Ar configuration.
That is, both Na+ and Cl have an octet of electrons
surrounding the central ion.
Ionic Bonding Arrangement
Energetics of Ionic Bond Formation

Lattice energy: the energy required to completely
separate an ionic solid into its gaseous ions.
Lattice energy depends on the charges on the ions and the
sizes of the ions:
Q1Q2
El
d
is a constant (8.99 x 10 9 Jm/C2), Q1 and Q2 are the
charges on the ions, and d is the distance between ions.
Electron Configurations of Ions of the

Representative Elements
These are derived from the electron configuration of
elements with the required number of electrons added or
removed from the most accessible orbital.
Electron configurations can predict stable ion formation:
Mg: [Ne]3s2
Mg+: [Ne]3s1
not stable
Mg2+: [Ne]
stable
Cl: [Ne]3s23p5
Cl: [Ne]3s23p6 = [Ar] stable
Transition Metal Ions and Polyatomic Ions

Transition Metal Ions
Lattice energies compensate for the loss of up to three
electrons.
In general, electrons are removed from orbitals in order
of decreasing n (i.e. electrons are removed from 4s
before the 3d).
Polyatomic Ions
Polyatomic ions are formed when there is an overall
charge on a compound containing covalent bonds. E.g.
SO42, NO3.
Covalent Bonding
When two similar atoms bond, none of them wants to
lose or gain an electron to form an octet.
When similar atoms bond, they share pairs of electrons to
each obtain an octet.
Each pair of shared electrons constitutes one chemical
bond.
Example: H + H H2 has electrons on a line connecting
the two H nuclei.
Covalent Bonding
Lewis Structures
Covalent bonds can be represented by the Lewis symbols
of the elements:
Cl + Cl
Cl Cl
In Lewis structures, each pair of electrons in a bond is
represented by a single line:
Cl Cl
H F
H O
H
H N H
H
H
H C H
H
Multiple Bonds
It is possible for more than one pair of electrons to be
shared between two atoms (multiple bonds):
One shared pair of electrons = single bond (e.g. H2);
Two shared pairs of electrons = double bond (e.g. O2);
Three shared pairs of electrons = triple bond (e.g. N2).
H H
O O
N N
Generally, bond distances decrease as we move from

single through double to triple bonds.
Bond Polarity and Electronegativity

In a covalent bond, electrons are shared.
Sharing of electrons to form a covalent bond does not
imply equal sharing of those electrons.
There are some covalent bonds in which the electrons are
located closer to one atom than the other.
Unequal sharing of electrons results in polar bonds.
Electronegativity
Electronegativity: The ability of one atoms in a
molecule to attract electrons to itself.
Pauling set electronegativities on a scale from 0.7 (Cs) to
4.0 (F).
Electronegativity increases
across a period and
down a group.
Electronegativity

Difference in electronegativity is a gauge of bond
polarity:
electronegativity differences around 0 result in non-polar
covalent bonds (equal or almost equal sharing of electrons);
electronegativity differences around 2 result in polar covalent
bonds (unequal sharing of electrons);
electronegativity differences around 3 result in ionic bonds
(transfer of electrons).

There is no sharp distinction between bonding types.
The positive end (or pole) in a polar bond is represented
+ and the negative pole -.
Dipole Moments
Consider HF:
The difference in electronegativity leads to a polar bond.
There is more electron density on F than on H.
Since there are two different ends of the molecule, we call HF
a dipole.
Dipole moment, , is the magnitude of the dipole:
Qr
where Q is the magnitude of the charges.

Dipole moments are measured in debyes, D.
Bond Types and Nomenclature

In general, the least electronegative element is named
first.
The name of the more electronegative element ends in
ide.
Ionic compounds are named according to their ions,
including the charge on the cation if it is variable.
Molecular compounds are named with prefixes.
Bond Types and Nomenclature

Ionic
Molecular
MgH2
Magnesium hydride H2S
Hydrogen sulfide
FeF2
Iron(II) fluoride
Oxygen difluoride
Mn2O3 Manganese(III)
oxide
OF2
Cl2O3 Dichlorine trioxide
Drawing Lewis Structures

1. Add the valence electrons of all atoms.
2. Write symbols for the atoms and show which atoms are
connected to which.
3. Complete the octet for all atoms bounded to the central
atom.
4. Place leftover electrons on the central atom even if it
results in more than an octet of electrons around the
atoms. (see section 8.7 for expanded octet rule)
5. If there are not enough electrons to give the central atom
an octet, try multiple bonds.
Formal Charge
It is possible to draw more than one Lewis structure with
the octet rule obeyed for all the atoms.
To determine which structure is most reasonable, we use
formal charge.
Formal charge is the charge on an atom that it would
have if all the atoms had the same electronegativity (i.e.,
if the electrons are shared equally between atoms).
Formal Charge
To calculate formal charge:
All nonbonding electrons are assigned to the atom on which

they are found.
Half the bonding electrons are assigned to each atom in a
bond.
Formal charge is:

valence electrons - number of bonds - lone pair electrons
Formal Charge
Consider:
C N
For C:
There are 4 valence electrons (from periodic table).

In the Lewis structure there are 2 nonbonding electrons and 3
from the triple bond. There are 5 electrons from the Lewis
structure.
Formal charge: 4 - 5 = -1.
Formal Charge
Consider:
C N
For N:
There are 5 valence electrons.

In the Lewis structure there are 2 nonbonding electrons and 3
from the triple bond. There are 5 electrons from the Lewis
structure.
Formal charge = 5 - 5 = 0.
We write:
C N
Formal Charge
The most stable structure has:
the lowest formal charge on each atom (i.e., closest to zero),

the most negative formal charge on the most electronegative
atoms.
Remember, formal charges are a way of bookkeeping and do not
represent the real charges on atoms.
The actual charge
distributions in molecules and ions are determined by a variety of
factors including the electronegativity difference in atoms.
Resonance Structures
Some molecules are not well described by Lewis Structures.

Typically, structures with multiple bonds can have similar
structures with the multiple bonds between different pairs of
atoms
Example: experimentally, ozone has two identical bonds whereas
the Lewis Structure requires one single (longer) and one double
bond (shorter).
Resonance structures are attempts to represent a real
structure that is a mix between several extreme
possibilities.
Example: in ozone the extreme possibilities have one
double and one single bond. The resonance structure
has two identical bonds of intermediate character.
O
O
O
O
Common examples: O3, NO3-, SO42-, NO2, and benzene.
Resonance in Benzene
Benzene consists of 6 carbon atoms in a hexagon. Each
C atom is attached to two other C atoms and one
hydrogen atom.
There are alternating double and single bonds between
the C atoms.
Experimentally, the C-C bonds in benzene are all the
same length.
Experimentally, benzene is planar.
Resonance in Benzene
We write resonance structures for benzene in which
there are single bonds between each pair of C atoms and
the 6 additional electrons are delocalized over the entire
ring:
or
Benzene belongs to a category of organic molecules

called aromatic compounds (due to their odor).
Exceptions to the Octet Rule

There are three classes of exceptions to the octet rule:
Molecules with an odd number of electrons;
Molecules in which one atom has less than an octet;
Molecules in which one atom has more than an octet.
Odd Number of Electrons

Few examples. Generally molecules such as ClO2, NO,
and NO2 have an odd number of electrons.
N O
N O
Less than an Octet

Relatively rare.
Molecules with less than an octet are typical for
compounds of Groups 1A, 2A, and 3A.
Most typical example is BF3.
Formal charges indicate that the Lewis structure with an
incomplete octet is more important than the ones with
double bonds.
More than an Octet

This is the largest class of exceptions.
Atoms from the 3rd period onwards can accommodate
more than an octet.
Beyond the third period, the d-orbitals are low enough in
energy to participate in bonding and accept the extra
electron density.
Strengths of Covalent Bonds

The energy required to break a covalent bond is called
the bond dissociation enthalpy, D. That is, for the Cl2
molecule, D(Cl-Cl) is given by H for the reaction:
Cl2(g) 2Cl(g).
When more than one bond is broken:
CH4(g) C(g) + 4H(g) H = 1660 kJ
the bond enthalpy is a fraction of H for the

atomization reaction:
D(C-H) = H = (1660 kJ) = 415 kJ.
Bond enthalpies can either be positive or negative.
Bond Enthalpies (kJ/mol)
Bond Enthalpies and the Enthalpies of

Reactions
We can use bond enthalpies to calculate the enthalpy for
a chemical reaction.
We recognize that in any chemical reaction bonds need
to be broken and then new bonds get formed.
The enthalpy of the reaction is given by the sum of bond
enthalpies for bonds broken less the sum of bond
enthalpies for bonds formed.

Reactions
Mathematically, if Hrxn is the enthalpy for a reaction,
then
H rxn D bonds broken D bonds formed
We illustrate the concept with the reaction between

methane, CH4, and chlorine:
CH4(g) + Cl2(g) CH3Cl(g) + HCl(g)
Hrxn = ?

Reactions
In this reaction one C-H bond and one Cl-Cl bond gets
broken while one C-Cl bond and one H-Cl bond gets
formed.
H rxn D C - H D Cl - Cl D C - Cl D H - Cl 104 kJ
The overall reaction is exothermic which means than the

bonds formed are stronger than the bonds broken.
The above result is consistent with Hesss law.
Bond Enthalpy and Bond Length

We know that multiple bonds are shorter than single
bonds.
We can show that multiple bonds are stronger than
single bonds.
As the number of bonds between atoms increases, the
atoms are held closer and more tightly together.
Strengths of Covalent Bonds

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Chapter 8

Basic Concepts of Chemical

Chemical Bonds, Lewis Symbols, and

The Octet Rule

Ionic Bonding Arrangement

Energetics of Ionic Bond Formation

Electron Configurations of Ions of the

Transition Metal Ions and Polyatomic Ions

Generally, bond distances decrease as we move from

Bond Polarity and Electronegativity

Bond Polarity and Electronegativity

Bond Polarity and Electronegativity

Dipole moment, , is the magnitude of the dipole:

where Q is the magnitude of the charges.

Bond Types and Nomenclature

Bond Types and Nomenclature

Magnesium hydride H2S

Cl2O3 Dichlorine trioxide

Drawing Lewis Structures

All nonbonding electrons are assigned to the atom on which

Formal charge is:

There are 4 valence electrons (from periodic table).

There are 5 valence electrons.

the lowest formal charge on each atom (i.e., closest to zero),

Some molecules are not well described by Lewis Structures.

Common examples: O3, NO3-, SO42-, NO2, and benzene.

Benzene belongs to a category of organic molecules

Exceptions to the Octet Rule

Odd Number of Electrons

Less than an Octet

More than an Octet

Strengths of Covalent Bonds

the bond enthalpy is a fraction of H for the

Bond Enthalpies (kJ/mol)

Bond Enthalpies and the Enthalpies of

Bond Enthalpies and the Enthalpies of

We illustrate the concept with the reaction between

Bond Enthalpies and the Enthalpies of

The overall reaction is exothermic which means than the

Bond Enthalpy and Bond Length

Strengths of Covalent Bonds

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