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Chapter 9: Chemical Bonding

Ionic compounds form when metals and


nonmetals react
The attraction between positive and
negative ions is called an ionic bond
The ionic compounds form because the
potential energy of the system decreases
Consider the example of sodium chloride
The energy change when NaCl forms can be
calculated using the ionization energy (IE)
of sodium, the electron affinity (EA) of
chlorine, and the lattice energy of NaCl

The energy needed to produce separated gaseous ions from


one mole of the solid is the lattice energy.
Starting from 1 mole of gas phase atoms:
Na(g) Na+(g) + e- +495.4 kJ (IE of sodium)
Cl(g) + e- Cl-(g) -348.8 kJ (EA of chlorine)
Na+(g)+Cl-(g)NaCl(s) -787.0 kJ (-lattice energy)
Net: -640.4 kJ
It turns out that for any ionic compound, the
chief stabilizing influence is the lattice
energy
The size of the lattice energy depends on
ion size and charge
The lattice energy increases with charge
because the ions attract each other more
strongly
Example: KCl (709 kJ) vs CaO (3401 kJ)
Smaller ions have larger lattice energies
because they get closer together
Example: NaCl (778 kJ) vs KCl (709 kJ) and LiF
(1033 kJ) vs LiCl (845 kJ)
The lattice energy can be calculated using a
Born-Haber cycle
A Born-Haber
cycle for NaCl.
The upper and
lower paths must
give the same
energy change
because enthalpy
is a state
function: both
paths lead from
the elements to
solid NaCl.
Noble gas configurations are very stable
and can be useful in predicting ion charges
Consider the case of sodium:
Na(g) Na+(g)+e- IE= 466 kJ/mol
Na+(g) Na2+(g)+e- IE=4563 kJ/mol
Na 1s22s22p63s1
Na+ 1s22s22p6 (noble gas core)
Na2+ 1s22s22p5
Formation of Na+ is relatively inexpensive
Na2+ doesnt (ordinarily) form because
breaking into the noble gas core costs a to much
energy
All noble gases (except He) have 8 valence
electrons
This is called an octet of electrons
Most of the representative elements tend to
gain or lose electrons until they have
achieved the configuration of the nearest
noble gas
For example: Na and K lose electrons to
achieve an octet of electrons while Cl and O
gain electron to achieve an octet of
electrons
The octet rule works best for ionic
compounds of Group IA and IIA metals
from Period 3 down and for the anions of
the nonmetals
It fails for Li and Be because they achieve
the He (1s2) electron configuration
It also doesnt work for hydrogen which can
form H- (electron configuration: 1s2) when
it reacts with very reactive metals
The octet rule doesnt work well for
transition metals and post transition metals
For these cations:
1) The first electrons lost by an atom or ion are
always those from the outer shell (with the
largest value of n)
2) Within a given shell: the f (subshell) is
emptied before the d, which is emptied before
the p, which is emptied before the s
Consider the case of iron:
Neutral: Fe [Ar]3d64s2
Loss of 4s electrons: Fe2+ [Ar]3d6
Loss of a 3d electron: Fe3+ [Ar]3d5
Many transition elements form multiple
cations (like iron)
Often, one of the cations has a charge of +2
The relative stability of the ions formed is
difficult to predict
Lewis symbols provide a convenient way to
keep track of valence electrons
In this notation the symbol of the element is
surrounded by dots (or similar symbols) that
represent the atoms valence electrons
Examples : Na and : C :
All the elements in a group have a similar
Lewis symbol because they have the same
number of valence electrons
Ions are treated in a similar fashion
Many substances comprised only of
nonmetals occur as molecules
Molecules involve electron sharing

Two hydrogen atoms (a) move together (b) until the


electron density is concentrated between the nuclei (c). This
is called a covalent bond.
Covalent bonds are characterized by their
bond distance, or average distance between
the nuclei, and the bond energy, or amount
of energy released when the bond forms
The energy of the
hydrogen molecule
reaches a minimum
when there is a
balance between the
attractions and
repulsions.
Lewis symbols can be used to represent the
covalent or electron pair bond
H HH:H
Both hydrogens are considered to have two
electrons
For simplicity, electron pair bonds are
usually represented by a dash
Example: hydrogen molecule is represented as H-H
Formulas drawn with Lewis symbols are
called Lewis formulas or Lewis structures
The term structural formula is also used
because it shows how the atoms in the
molecule are attached to each other
Many molecules obey the octet rule:
When atoms form covalent bonds, they tend to
share sufficient electrons so as to achieve an
outer shell having eight electrons
In most of their covalently bonded
compounds, the number of covalent bonds
formed by carbon, nitrogen, and oxygen are
four, three, and two, respectively
One shared pair of electrons is called a
single bond
Double and triple bonds are also common:

Examples : carbon dioxide : O C O



:
nitrogen : N N :
Organic compounds will frequently be used
as examples later in the text
In general, organic compounds are held
together with covalent bonds
The simplest hydrocarbons are the alkanes
with the general formula CnH2n+2
The first three alkanes are methane, ethane,
and propane
In condensed form they are written:
methane: CH4
ethane: CH3CH3
propane: CH3CH2CH3
Things get more complicated starting with
alkanes containing four carbons
butane : CH 3CH 2 CH 2 CH 3 bp - 0.5C
isobutane : CH 3CHCH 3 bp - 11.7C
|
C H3
Hydrocarbons that contain one double bond
have the general formula CnH2n and are
called alkenes
Hydrocarbons that contain one triple bond
have the general formula CnH2n-2 and are
called alkynes
ethene : CH 2 CH 2 (also called ethylene)
ethyne : CH CH (also called acetylene)
Most organic compounds contain elements
in addition to carbon and hydrogen
These are considered to be hydrocarbon
derivatives
Using the symbol R to represent any
hydrocarbon fragment (such as CH3-, or
CH3CH2-) important families include:
General
Name Formula Example
Alcohols R OH CH 3 OH (methyl alcohol)
O O
|| ||
Aldehydes R C H CH 3 C H (acetaldeh yde)
O O
|| ||
Acids R C OH CH 3 C OH (acetic acid)
Amines R NH 2 CH 3 NH 2 (methyl amine)
R NH R
R N R
|
R
Ball and stick models are common
When two identical atoms form a covalent
bond each atom has an equal share of the
bonds electron pair
When different kinds of atoms combine,
one nuclei usually attracts the electrons in
the bond more strongly
(a) The electron density of the
electron pair in the bond is
spread evenly between the
two H atoms in H2, which
gives a nonpolar covalent
bond.
(b) The electron density of the
bond in HCl is pulled more
tightly around the Cl end of
the molecule giving a partial
separation of charge and a
polar covalent bond.
The magnitude of the polarity is expressed
in terms of the dipole moment
dipole moment q r
q amount of charge
r distance between charges
Dipole moments are frequently reported in
units of Debye (D)
1 D 3.34 10-30 C m
The dipole moments and bond lengths for
some diatomic molecules are:
Dipole Bond
Compound Moment(D) Length(pm)
HF 1.83 91.7
HCl 1.09 127
HBr 0.82 141
HI 0.45 161
CO 0.11 113
NO 0.16 115
Electronegativity is the term used to
describe the relative attraction of an atom
for the electrons in a bond
The element with the larger
electronegativity will carry the partial
negative charge
The difference in electronegativity provides
an estimate for the degree of polarity of the
bond
There is no sharp dividing line between
ionic and covalent bonding: ionic bonding
and nonpolar covalent bonding represent the
extremes
A bond is mostly ionic when the
electronegativity difference between the
two atoms is large
The degree of polarity, or ionic character, varies
continuously with the electronegativity difference

Each atom in a
bond has a partial
charge of about
+0.5 or 0.5 units
when the
electronegativity
difference is 1.7.

In general, electronegativity increases bottom to


top in a group and left to right in a period
Metal reactivity refers to the tendency of
the metal to undergo oxidation
The lower the electronegativity the easier a
metal is to oxidize
Metals that are
most easily
oxidized are
found on the far
left of the periodic
table.
For nonmetals, reactivity is usually gauged
by the ability to act as an oxidizing agent
In general, the oxidizing ability of
nonmetals increases from left to right in a
period and bottom to top in a group
This makes fluorine, found in the upper
right of the periodic table, the strongest
oxidizing agent
Single displacement reactions may be
predicted from nonmetal reactivity
Consider the halogens (Group VIIA): a
halogen as an element will oxidize the anion
of any halogen below it
F2 will oxidize Cl-, Br-, and I-
Example: F2 + 2Cl- 2F- + Cl2
Cl2 will oxidize Br- and I-
Example: Cl2 + 2Br- 2Cl- + Br2
Br2 will oxidize I-
Example: Br2 + 2I- 2Br- + I2
Lewis structures are useful because they
give a simple way to describe the structure
of molecules
Not all structures obey the octet rule
Most nonmetals beyond Period 2 form
structures with more than eight electrons
Examples: PCl5 and SF6
In some compounds the central atom has
less than eight electrons
Common examples include compounds of
beryllium and boron
Examples: BeCl2 and BCl3
Summary of steps in
writing Lewis Structures.
Following these steps
will produce a Lewis
structure in which the
octet rule is obeyed by
the maximum number of
atoms. Remember for
ions to add one electron
for each negative charge
and to remove one
electron for each positive
charge.
Lewis structures describe how atoms share
electrons in chemical bonds
The bond length and bond energy are
related to the number of electron pairs
shared between to atoms
The hydrogen
molecule has a
bond length of 75
pm and a bond
energy of 435
kJ/mol.
For bonds between the same elements the
bond length and bond energy depend on the
bond order
The bond order is the number of pairs of
electrons shared between two atoms
A single bond has bond order of 1; a double
bond a bond order of 2; and a triple bond a
bond order of 3
The bond order is a measure of the amount
of electron density in a bond
More electron density gives a stronger bond
Consider the average bond lengths and bond
energies for carbon-carbon bonds:
Bond Bond
Bond Length(pm) Energy(kJ/ mol)
CC 154 348
CC 134 615
CC 120 812
Bond lengths and bond energies are
obtained from experiment
The preferred Lewis structure is the one that
best fits the experimental data
The structure of sulfuric acid in
the vapor state. There are two
different sulfur-oxygen bond
lengths. The preferred Lewis
structure needs different bond
orders for these atoms.

The preferred Lewis structure for sulfuric


acid violates the octet rule:

:O: :O:
| ||

HO

S O

H HO

S O

H
| ||
:O

: :O:
Structure I Structure II
Structure I obeys the octet rule, but is not
consistent with experiment
Structure II violates the octet rule, but is
consistent with experiment
Structure II is the preferred Lewis structure
Formal charge is the apparent charge on an
atom
The formal charge on a atom is calculated
by subtracting the number of valence
electrons assigned to it in a Lewis structure
from the number of valence electrons in an
isolated atom
formal valence e on number of bonds number of
charge

isolated atom to the atom unshared e
Consider the sulfur atoms in the two
structures for sulfuric acid:
Structure I: formal charge on S = 6 - (4 + 0) = +2
Structure II: formal charge on S = 6 - (6 + 0) = 0
When several Lewis structures are possible,
those with the smallest formal charges are
the most stable and preferred
Note that the formal charges for all atoms in
a Lewis structure sum to the charge on the
species
Some molecules and ions are not well
represented by a single Lewis structure
Consider the case of the formate ion
Experiment gives a single carbon-oxygen
bond length
A combination of structures is needed to
describe this ion
These are called resonance structures and
the ion is said to be a resonance hybrid of
the contributing structures




:O :
:O :

H C O : H C O :
|| |






Two resonance structures are required for
the formate ion because two equivalent
carbon-oxygen double bonds can be formed
Note that three resonance structures would
be required to represent SO3
The total energy of a resonance hybrid is
lower in energy than any one of its
resonance structures
This energy lowering is called the
resonance energy
Benzene has a planar
hexagonal structure and is
a resonance hybrid of
resonance structures. Its
resonance energy is about
146 kJ/mol.
Consider the formation of the ammonium
ion from ammonia and a hydrogen ion in
solution

H H
|
|

H N : H H N H
| |

H H
The nitrogen donates both of the electrons
when forming the bond to H+
This is called a coordinate covalent bond
The concept of a coordinate bond can be
useful when trying to understand what
happens to atoms in reactions
For example, addition compounds involve
coordinate covalent bonds and can result
when two small molecules join

H :Cl: H :Cl:
| | | |

H N : B Cl

: H N B Cl

:
| | | |
H :Cl:
H :Cl: