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• The energy change when NaCl forms can be

Chapter 9: Chemical Bonding calculated using the ionization energy (IE)
of sodium, the electron affinity (EA) of
• Ionic compounds form when metals and chlorine, and the lattice energy of NaCl
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 needed to produce separated gaseous ions from
one mole of the solid is the lattice energy.

• Starting from 1 mole of gas phase atoms: – The lattice energy increases with charge
Na(g) Æ Na+(g) + e- +495.4 kJ (IE of sodium) because the ions attract each other more
Cl(g) + e- Æ Cl-(g) -348.8 kJ (EA of chlorine) strongly
Na+(g)+Cl-(g)ÆNaCl(s) -787.0 kJ (-lattice energy) • Example: KCl (709 kJ) vs CaO (3401 kJ)
Net: -640.4 kJ
– Smaller ions have larger lattice energies
• It turns out that for any ionic compound, the because they get closer together
chief stabilizing influence is the lattice • Example: NaCl (778 kJ) vs KCl (709 kJ) and LiF
energy (1033 kJ) vs LiCl (845 kJ)

• The size of the lattice energy depends on • The lattice energy can be calculated using a
ion size and charge Born-Haber cycle

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• Noble gas configurations are very stable

A Born-Haber and can be useful in predicting ion charges
cycle for NaCl. – Consider the case of sodium:
The upper and
Na(g) Æ Na+(g)+e- IE= 466 kJ/mol
lower paths must
give the same Na+(g)Æ Na2+(g)+e- IE=4563 kJ/mol
energy change Na 1s22s22p63s1
b
because enthalpy
th l Na+ 1s22s22p6 (noble gas core)
is a state Na2+ 1s22s22p5
function: both – Formation of Na+ is relatively inexpensive
paths lead from
– Na2+ doesn’t (ordinarily) form because
the elements to
solid NaCl.
breaking into the noble gas core costs a to much
energy

• All noble gases (except He) have 8 valence • The octet rule works best for ionic
electrons
compounds of Group IA and IIA metals
• This is called an octet of electrons from Period 3 down and for the anions of
• Most of the representative elements tend to the nonmetals
gain or lose electrons until they have
achieved the configuration of the nearest • It fails for Li and Be because they achieve
noble gas th He
the (1 2) electron
H (1s l t configuration
fi ti
• For example: Na and K lose electrons to • It also doesn’t work for hydrogen which can
achieve an octet of electrons while Cl and O form H- (electron configuration: 1s2) when
gain electron to achieve an octet of it reacts with very reactive metals
electrons

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• The octet rule doesn’t 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: • Lewis symbols provide a convenient way to

Neutral: Fe [Ar]3d64s2
Loss of 4s electrons: Fe2+ [Ar]3d6
Loss of a 3d electron: Fe3+ [Ar]3d5
• Manyy transition elements form multiplep
cations (like iron)
• Often, one of the cations has a charge of +2
• The relative stability of the ions formed is
difficult to predict
keep track of valence electrons
• In this notation the symbol of the element is
surrounded by dots (or similar symbols) that
represent the atom’s valence electrons
E
Examples
l : Na
N • andd : C :
• All the elements in a group have a similar
Lewis symbol because they have the same
number of valence electrons

3

• 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.
• Lewis symbols can be used to represent the
covalent or electron pair bond
H•+•H→ H: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
11/9/2009
• 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
h drogen molec
hydrogen molecule
le
reaches a minimum
when there is a
balance between the
attractions and
repulsions.
• 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
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• One shared pair of electrons is called a • The simplest hydrocarbons are the alkanes
single bond with the general formula CnH2n+2
• Double and triple bonds are also common: • The first three alkanes are methane, ethane,
••

Examples : carbon dioxide : O = C = O : and propane

••

nitrogen : N ≡ N : • In condensed form they are written:

methane: CH4
• Organic compounds will frequently be used
ethane: CH3CH3
as examples later in the text
propane: CH3CH2CH3
• In general, organic compounds are held
together with covalent bonds • Things get more complicated starting with
alkanes containing four carbons

butane : CH 3CH 2CH 2 CH 3 bp = - 0.5°C ethene : CH 2 = CH 2 (also called ethylene)

isobutane : CH 3CHCH 3 bp = - 11.7°C ethyne : CH ≡ CH (also called acetylene)
|
C H3 • Most organic compounds contain elements
• Hydrocarbons that contain one double bond in addition to carbon and hydrogen
have the ggeneral formula CnH2n and are • These are considered to be hydrocarbon
called alkenes derivatives
• Hydrocarbons that contain one triple bond • Using the symbol “R” to represent any
have the general formula CnH2n-2 and are hydrocarbon fragment (such as CH3-, or
called alkynes CH3CH2-) important families include:

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General
• Ball and stick models are common
Name Formula Example
Alcohols R − OH CH 3 − OH (methyl alcohol)
O O
|| ||
Aldehydes R − C − H CH 3 − C − H (acetaldehyde)
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

(a) The electron density of the

electron pair in the bond is
• When two identical atoms form a covalent spread evenly between the
bond each atom has an equal share of the two H atoms in H2, which
bond’s electron pair gives a nonpolar covalent
bond.
• When different kinds of atoms combine,, (b) The electron density of the
one nuclei usually attracts the electrons in bond in HCl is pulled more
tightly around the Cl end of
the bond more strongly the molecule giving a partial
separation of charge and a
polar covalent bond.

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Dipole Bond
• The magnitude of the polarity is expressed Compound Moment(D) Length(pm)
in terms of the dipole moment HF 1.83 91.7
dipole moment = μ = q × r HCl 1.09 127
q = amount of charge HBr 0.82 141
r = distance between charges HI 0.45 161
CO 0.11 113
• Dipole
p moments are frequently
q y reported
p in
NO 0.16 115
units of Debye (D)
• Electronegativity is the term used to
1 D = 3.34 × 10-30 C m describe the relative attraction of an atom
• The dipole moments and bond lengths for for the electrons in a bond
some diatomic molecules are:

• The difference in electronegativity provides

• The element with the larger
electronegativity will carry the partial
negative charge
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

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• The degree of polarity, or ionic character, varies

• Metal reactivity refers to the tendency of
continuously with the electronegativity difference
the metal to undergo oxidation
Each atom in a • The lower the electronegativity the easier a
bond has a partial
charge of about metal is to oxidize
+0.5 or –0.5 units Metals that are
when
h theh most easily
electronegativity oxidized are
difference is 1.7. found on the far
left of the periodic
• In general, electronegativity increases bottom to table.
top in a group and left to right in a period

• 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- Æ 2F- + Cl2
– Cl2 will oxidize Br- and I-
• Example: Cl2 + 2Br- Æ 2Cl- + Br2
– Br2 will oxidize I-
• Example: Br2 + 2I- Æ 2Br- + I2
• Lewis structures are useful because they
give a simple way to describe the structure
of molecules

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• Not all structures obey the octet rule

Summary of steps in
• Most nonmetals beyond Period 2 form writing Lewis Structures.
structures with more than eight electrons Following these steps
will produce a Lewis
• Examples: PCl5 and SF6 structure in which the
• In some compounds the central atom has octet rule is obeyed by
the maximum number of
l than
less th eight
i ht electrons
l t atoms. Remember for
• Common examples include compounds of ions to add one electron
for each negative charge
beryllium and boron
and to remove one
• Examples: BeCl2 and BCl3 electron for each positive
charge.

• Lewis structures describe how atoms share • For bonds between the same elements the
electrons in chemical bonds bond length and bond energy depend on the
• The bond length and bond energy are bond order
related to the number of electron pairs • The bond order is the number of pairs of
shared between to atoms electrons shared between two atoms
The hydrogen • A single
i l bond
b d has
h bond
b d order
d off 1;
1 a double
d bl
molecule has a bond a bond order of 2; and a triple bond a
bond length of 75
pm and a bond
bond order of 3
energy of 435 • The bond order is a measure of the amount
kJ/mol.
of electron density in a bond

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• More electron density gives a stronger bond • The preferred Lewis structure is the one that
• Consider the average bond lengths and bond best fits the experimental data
energies for carbon-carbon bonds: The structure of sulfuric acid in
Bond Bond the vapor state. There are two
Bond Length(pm) Energy(kJ/ mol) different sulfur-oxygen bond
C−C 154 348 g
lengths. The preferred
p Lewis
structure needs different bond
C=C 134 615
orders for these atoms.
C≡C 120 812
• Bond lengths and bond energies are • The preferred Lewis structure for sulfuric
obtained from experiment acid violates the octet rule:

••

:O: :O: • Formal charge is the apparent charge on an

•• | •• •• || ••

H−O − S −O −H H−O − S −O −H atom

•• ••
| •• ••
||
:O : :O: • The formal charge on a atom is calculated
••
by subtracting the number of valence
Structure I Structure II electrons assigned to it in a Lewis structure
• Structure I obeysy the octet rule,, but is not from the number of valence electrons in an
consistent with experiment isolated atom
• Structure II violates the octet rule, but is
⎡formal⎤ ⎡ valence e − on ⎤ ⎡number of bonds + number of ⎤
consistent with experiment ⎢charge⎥ = ⎢ ⎥−⎢ ⎥
⎣ ⎦ ⎣isolated atom ⎦ ⎣⎢ to the atom unshared e − ⎦⎥
• Structure II is the preferred Lewis structure

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• 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

−
⎡ ⎤
••
− • The total energy of a resonance hybrid is
⎡ :O: ⎤ ⎢
:O:
⎥
⎢H − C − O :⎥ ↔ ⎢H − C = O :⎥
|| •• | lower in energy than any one of its
⎢ •• ⎥
⎢
••
⎥
resonance structures
⎣⎢ ⎦⎥ ⎢⎣ ⎥⎦ • This energy lowering is called the
resonance energy
q
• Two resonance structures are required for Benzene has a planar
the formate ion because two equivalent hexagonal structure and is
a resonance hybrid of
carbon-oxygen double bonds can be formed resonance structures. Its
• Note that three resonance structures would resonance energy is about
be required to represent SO3 146 kJ/mol.

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• Consider the formation of the ammonium • The concept of a coordinate bond can be
ion from ammonia and a hydrogen ion in useful when trying to understand what
solution happens to atoms in reactions
+
H ⎡ H ⎤ • For example, addition compounds involve
|
⎢ |
⎥
H − N : + H + → ⎢H − N − H ⎥ coordinate covalent bonds and can result
| |
⎢ ⎥ when
h ttwo smallll molecules
l l “join”
“j i ”
H ⎣ H ⎦
•• ••
• The nitrogen donates both of the electrons H :Cl: H :Cl:
| | | |
when forming the bond to H+ ••

H − N : + B − Cl
••

:→ H − N − B − Cl :
| | •• | | ••
• This is called a coordinate covalent bond
H :Cl:••
H :Cl:
••

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