General Chemistry I LECTURE NOTES Kelly

Chapter 8: Inside Materials: Chemical Bonds

Ionic Bonding
Inert Gas Configuration; Octet Rule. Certain elements in the periodic table are especially
stable. These are the inert gases, helium, neon, argon,krypton, xenon and radon found in group
8A. The common features of these elements is that they all have a completely filled valence
shell of electrons. Except for helium which has a filled shell of two electrons, all the remaining
inert gases have 8 electrons in their outer shell. This special configuration can also be attained
in other elements; it is the major driving force in the formation of ions (by gain or loss of
electrons). Elements or ions which have a filled shell of electrons are said to obey the octet rule.
Elements at the left of the periodic table (like groups 1A and 2A) can most easily attain a filled
shell configuration by donating electrons. Conversely, elements on the right side of the periodic
table are converted to the octet configuration by accepting electrons.

Formation of ions. Much of chemistry can be understood in terms of the various elements' wish
to gain the filled shell configuration. In the reaction of sodium with chlorine gas, both elements
can satisfy the octet rule by transfer of one electron from the sodium to the chlorine. During
this process the chlorine becomes a chloride anion, the sodium a sodium cation. Both ions have
a filled shell, noble gas configuration.

The sodium half-reaction): Same electronic

configuration as Ne
Na (1s2 2s 2 2p6 3s1) 1 e- + Na + (1s22s2 2p6)

Elemental sodium, available

a source of one electron
electron
Thechlorine half-reaction Same electronic
configuration as Ar
Cl (1s 2 2s 2 2p6 3s2 3p 5) + 1 e- Cl- (.....3p6)

Elemental chlorine, electron

an acceptor of one needed
electron
Filled shell configuration by loss or gain of electrons

What about the energy change, E, that occurs when sodium and chlorine react to yield Na + and
Cl-? Lets begin by comparing the Ionization Potential Ip for sodium and the Electron Affinity
Ea for Chlorine:
Ip for Na = +495.8 kJ/mole unfavorable
Ea for Cl = - 348.6 kJ/mole favorable
E = +147.2 kJ/mole unfavorable
Thus the net reaction of Cl and Na would be unfavorable and no reaction would occur, unless
there is some other factor involved.
The additional factor which overcomes the unfavorable energy factor of electron transfer is the
large gain in stability due to the formation of ionic bonds. This energy term is called the
LATTICE ENERGY.

The actual reaction of sodium with chlorine occurs all at once, but the overall reaction can be
broken down into a series of hypothetical steps for which experimentally measured energy
values can be obtained. A pictorial way of viewing the hypothetical steps in a reaction is called
a BORN-HABER CYCLE, which shows how each step contributes to the overall energy
change. The Born-Haber cycle for sodium chloride is shown below.

4
Na(s) +1/2 Cl 2(g) Na+ (g) + e- + Cl(g) Na+(g) + e- + Cl(g) Na +(g) + Cl- (g)
3
E = +496 kJ/mol E = -349 kJ/mol

Na(s) +1/2 Cl 2(g) Na(g) + Cl(g) 2

E = +122 kJ/mol

Na(s) +1/2 Cl 2(g) Na(g) + 1/2Cl2(g) 1 5 Na+(g) + Cl- (g) NaCl(s)

E = +107 kJ/mol START HERE E = -787 kJ/mol

Na(s) + 1/2Cl2(g) NaCl(s) 6

H f = -411 kJ/mole

The Born-Harber cycle above has 6 components:

1. The energy required to convert solid sodium metal to the gas phase is called the
Enthalpy of Atomiztion. This is the heat energy required transform sodium from
its form at standard conditions (solid at 25C) to the gas phase.
2. The energy required to convert 1/2 mole of chlorine molecules to one mole of
chlorine atoms. To do this the Cl-Cl bond must be broken. The energy required
for this is called the Bond Dissociation Energy (D). The D for molecular
chlorine is 244 kJ/mole
3. Ionization of sodium atoms in the gas pahse. The energy for this is simply the first
Ionization Potential for Na.
4. Formation of chloride anion form chlorine atom by the addition of an electron.
This is simply the Electron Affinity of the chlorine atom.
5. Formation of NaCl(s) from isolated Na+ and Cl- in the gas phase. The energy
change for this step is a measure of the overall electrostatic potential between ions
in the solid. The usm of the electrostatic interactions between ions in the solid is
called the LATTICE ENERGY. The magnitude of the lattice energy is described
 by Coulombs Law and is equal to a constant k times the product of the charge on
the ions q+,q-, divided by the distance between their centers, d
+
q q
LatticeEnergy = U = k
d
6. The NET REACTION is simply the Enthalpy of Formation, Hf when the ionic
compound is formed from its elements in their standard states.

EXAMPLE 1
Calculate the Heat of Formation, Hf , of MgCl2 using the following information:
Heat of atomization of Mg =148 kJ/mole D for Cl2 = 244 kJ/mole
First Ip for Mg = 738 kJ/mole Second Ip for Mg = 1451 kJ/mole
Lattice Energy for MgCl2 = -2524 kJ/mole Ea for Cl = -349 kJ/mole

Solution:
Set up a Born-Haber cycle:

5 Mg +2(g) +2 e - + 2Cl(g) Mg +2(g) + e- + Cl- (g) + Cl(g)

Ea = - 349 kJ/mol

4
Mg +(s) +Cl2(g) Mg+2 (g) +2 e- + 2Cl(g)
2nd Ip = +1451 kJ/mol 5 Mg+2 (g) + e- + Cl-(g) + Cl(g) Mg +2(g) + 2Cl-(g)
a = - 349 kJ/mol

Mg(s) +Cl2 (g) Mg+(g) + e - + 2Cl(g) 3

1st Ip = +740 kJ/mol
Mg+2 (g) + 2Cl- (g) MgCl2(s)
6 U = -2524 kJ/mol
Mg(s) +Cl2 (g) Mg(g) + 2Cl(g) 2
E = +244 kJ/mol

Mg(s) +Cl2 (g) Mg(g) + Cl2(g) 1

E = +148 kJ/mol
START HERE

Mg(s) + Cl2(g) MgCl2(s)

Hf =?

Hf = 1 + 2 + 3 + 4 + 2(5) +6
Hf = [148 +244 +740 + 1451 + 2(-349) + (-2524)]kJ/mole
Hf = -639 kJ/mole
Covalent Bonding.

Not all compounds are comprised of ions. In particular, many carbon compounds are not ionic.
The reason for this difference can be found in the electronic configuration of carbon
(1s2,2s2,2px1,2py1). To gain a filled shell configuration, carbon would have to either gain or
lose four electrons. This represents an energetically unfavorable situation. But since millions
of compounds exist which contain bonds between carbon and other elements an alternative to
ionic bonding must exist

The solution to the bonding problem posed by carbon is to share electrons in a covalent bond.
This type of bonding was proposed by G. N. Lewis in 1916. The formalism depicts bonds
resulting from having a pair of nuclei being shared between two nuclei. The models resulting
from this formalism are called Lewis Structures. This model is the cornerstone of understanding
organic reaction mechanisms and is exceptionally useful for electronic bookkeeping. The
covalent bond between the two hydrogen atoms in the diatomic hydrogen molecule (H2) is
shown below.

Imagine the situation as the two hydrogen atoms are brought into close proximity. Each atom is
surrounded by regions of space where there is a high probability of finding an electron (atomic
orbitals). Hydrogen in its ground state has an electron in the spherical 1s orbital. The 1s
orbitals begin to overlap as the atoms are brought together and in the overlap region between
the two hydrogen nuclei there is a higher probability of find both electrons (the probability
wavefunctions that define each 1s atomic orbital add together in a constructive manner).

The covalent H-H bond is the net result of attractive and repulsive electrostatic forces. The
nucleus-electron attractive forces are greater than the nucleus-nucleus and electron-electron
repulsive forces, resulting in a net attractive force that holds the atoms together to form an H2
molecule. In essence, the two shared electrons act as a kind of glue to bind the two nuclei
together. Both nuclei are simultaneously attracted to the same electrons and are there fore held
together, much as two tug-of-war teams pulling on the same rope are held together.
As you might expect, the magnitude of the attractive and repulsive forces between nuclei in a
covalent bond depend on how close the atoms are. If the atoms are two far apart, there is no
overlap between the atomic orbitals, the electron do no reside in the region of space between the
two nuclei and no bond exists. Conversely, if the nuclei are two close together, the nucleus-
nucleus repulsion becomes so strong that it pushes the atoms apart. There is an optimum point
where the attractions are maximized, the repulsions are minimized and the molecule is most
stable. The optimum distance between nuclei is called BOND LENGTH. Shown below is a
graph of energy versus internuclear distance for the H2 molecule.

Lewis (electron dot) Structures

One of the most convenient ways of depicting the sharing of valence electrons between
covalently bonded atoms is to use what are known as Lewis, or electron-dot, structures. An
electron dot structure represents an elements valence electrons by dots and the placement of
these dots illustrates how the electrons are distributed in a molecule.

Writing Lewis Structures

i. Start with a central atom (usually the element with the lowest ionization potential,
or the element present in the fewest numbers, if carbons are present make them the
central atoms).
 ii. Place all the outer shell electrons on four imaginary sides. Don't pair
electrons unless more than four are in the outer shell of an atom.
iii. Bring the other atoms of the molecule in to the central atom so that single
electrons on the central atom can be paired with single electrons on the other
atoms.
iv. If, after all atoms have been added, two adjacent atoms have unshared
electrons, they share the unshared electrons to make multiple bonds.
v. If the species is an ion, then add or subtract the appropriate number of
electrons in order to obtain the charge of the ion.
vi. The final Lewis-dot structure should have eight electrons around all atoms
except hydrogen , which has two. (There are a few exceptions to the octet
rule but these involve 3rd row elements such as phosphorus and sulfur.

Covalent Bonding in methane

H H
C + 4H H C H or H C H
H H
Note that the hydrogen of methane have a helium closed shell and the
carbon has a neon closed shell
LEWIS STRUCTURES FOR COVALENT MOLECULES

Unshared pairs. Not all electrons in a covalent compound are necessarily involved in bonding;
some structures have orbitals that contain unshared pairs of electrons. While these electrons are
not used in determining the primary bonding arrangement of the covalent compound, they are
of basic importance in determining how the compound will react in later reactions. In drawing
Lewis Structures, the non-bonding pairs are often not shown, but we shall draw them explicitly
at this stage of the course. Lewis Structures are also useful in understanding the bonding of
covalent compounds containing multiple bonds (double and triple).

H H
H C O C H H 3C O CH3 dimethyl
H ether
H
unshared pairs
H H 3C
C O C O formaldehyde
H H 3C
Lewis structures with unshared pairs and/or multiple bonds

The tendency of Main-Group elements to fill their s and p subshells when they form covalent
bonds the OCTET RULE is a guiding principle that makes it possible to predict the
formulas and electron dot structures of many compounds. For second row elements, in
particular, the following rules apply:
 Group 13 Elements such as boron have three valence and can form three electron pair
bonds. Thus the Boron atom in the resultant molecule has only six valence electrons and
cannot for an octet.

Group 14 Elements such as carbon have four valence electrons and can form four
covalent bonds.

Group 15 Elements such as nitrogen have five valence electrons and can form three
bonds, with a pair of non-bonding (lone-pair) electrons.

Group 16 Elements such as oxygen have six valence electrons and can form two bonds,
with two pairs of non-bonding electrons.

Group 17 Elements such as fluorine have seven valence electrons and can form one
covalent bond with three pairs of non-bonding electrons.

Multiple Bonds
Not all covalent molecules share just a single pair of bonding electrons. In diatomic nitrogen
and oxygen, three and two pairs of bonding electrons are shared respectively as is shown below:

N + N N N N N N N
Incomplete octet Incomplete octet
share two more share two more
electrons electrons

N N Nitrogen
Triple Bond
O + O O O O O
Incomplete octet
share two more
electrons

O O Oxygen
Double Bond
In speaking of multiple bonds we use the term BOND ORDER to refer to the number of
electron pairs shared between the atoms. Thus , the oxygen-oxygen bond in O2 has a bond
order of two, while the nitrogen-nitrogen bond in N2 has a bond order of three.

As you might expect, multiple bonds are both shorter and stronger than their single counterparts
because there are more shared electrons holding the nuclei together. For example:
 H H
O O H O O H N N H N N H
Bond Length 121 pm 148 pm 110 pm 145 pm

Bond 498 213 945 275

Strength (kJ/mole)

Expanded Octets
The simple method of drawing electron-dot structures that works so well for compounds of
second row elements, sometimes breaks down for compounds of third row elements. Elements
in the third row an lower have unfilled orbitals in the d subshell which are available and can
therefore expand their valence shell beyond the normal octet, forming more than the normal
number of bonds that would be explained by the octet rule. In bromine trifluoride BrF3, for
example, the bromine forms three two-electron covalent bonds rather than one and has ten
electrons in its valence shell rather than eight.
BrF3 # valence electrons
Br..................7
3 F...............21
TOTAL.......28
Begin by placing all
28 electrons around F F
the atoms....Notice F Br F
that all the octets are F Br F
filled by 26 electrons
+ 2 electrons
left over!
Bromine, being a third row element with low lying 3d
orbitals can expand its octet to over eight electrons

F
F F
Br

Formal Charge
The Lewis structures we have drawn thus far have all been neutral covalent molecules.
However, some covalently bonded molecules may contain charged atomic components.
Furthermore, many ionic species also contain covalent bonds. To manage the electronic
bookkeeping we assign a formal charge to each of the atoms of a structure. The formula ,
Formal Charge = Valence Electrons - 1/2( Bonding Electrons) - Non-Bonding Electrons will
be used for this purpose.

H +
For Nitrogen For Hydrogen

H N H FC = VE-(1/2BE + NBE) FC = VE-(1/2BE + NBE)

FC = 5 - ( 8/2 + 0) = 1 FC = 1 - (2/2 + 0) = 0
H

Nitrogen bears the positive charge

Calculation of Formal Charge

Resonance Structures
Resonance structures are groups of Lewis-type representations which differ only in the position
of localized electron density. A resonance structure is a formula which can be written which
involves the movements of bonds, unshared electron pairs, single electrons or charges. It is
important to understand that atoms stay fixed in space in resonance structures, only electrons
are shared over one atom. Structures which involve the movement of atoms are not valid
resonance forms. The standard rules for writing valid Lewis structures (octet rule, no
pentavalent carbons, etc.) apply for resonance forms.
Two possible Lewis Structures for the acetate ion: CH3COO

- 1/2
O a O a O
H C H C H C
C O b C O b C O - 1/2
H H H H H H
For Oxygen a: FC = 0 FC = -1 Each Oxygen has a -1/2
For Oxygen b: FC = -1 FC = 0 Formal Charge. The one
double bond is shared.
RESONANCE STRUCTURES RESONANCE HYBRID

DO NOT USE TWO SINGLE

ARROWS, THIS DEPICTS
AN EQUILIBRIUM

Use of Double-Headed Arrows to indicate Resonance Structures

The formalism used to depict resonance structures is the double-headed arrow. This must be
well-understood to be distinct from the pair of single headed arrows used to describe an
equilibrium reaction. It must be remembered that while we may draw several separate
structural formulae to depict the various resonance contributors, these are not individual
molecules in equilibrium with one another, but a composite depiction of the chemicalspecies
being discussed.
A molecule is a weighted average of all its contributing resonance structures. The structural
depiction of the weighted average is called the Resonance Hybrid. The best real world
analogy for a resonance hybrid would be to consider a biological hybrid formed when two
related species form offspring. A good example of this is the mule, a hybrid formed in the
crossing of a horse and a donkey. A mule is always a mule, it show some characteristics of
horses and some of donkeys, but it is always a mule. It never spends part of its time as a horse
and part of its time as a donkey ( this would be like equilibrium).

While a molecule is an average of its contributing resonance structures, it need not be true that
all resonance forms contribute equally. To assess the weighting of the contributions we
examine the various structures and consider their stability as if they were real individual
molecules ( which , of course, they are not). The forms that have the greatest stability are the
forms which have the greatest contribution to the resonance hybrid.
1. Identical structures contribute equally.
H H H H
H C C H C C
H C H C
H H
2. Structures with the greater number of bonds are more important

H H H H H H
C C C C C C
H H H H H H
BEST

3. Structures that delocalize charge or unshared electrons are important

H H
H C O C H H C O C H
H H H H
BETTER
4. When considering structures with separated charges, atoms with
appropriate electronegativity will best accomodate the charges.

H H
H C C O H C C O

H H H H
BETTER
Rules for Writing Resonance Structures
Example 2:
Draw all the valid Lewis Structures for the following compounds, indicate the resonance
structures by means of a double headed arrow and draw a circle around the structure
which contributes most to the resonance hybrid: a) cyanate ion CNO-, b) ozone 03

Solution:
a)
CNO- # Valenec Electrons
C...........................4
N...........................5
O...........................6
-1 charge........... 1
TOTAL............. 16
share
non-bonding
-1 -1
electrons
N C O N C O N C O
Not a Valid
Lewis Structure Negative charge on
incomplete octets atom with greater
Electron affinity
b)
O3 # Valenec Electrons
3 x O.................18
share
non-bonding
-1 +1 +1 -1
electrons
O O O O O O O O O
Not a Valid
Lewis Structure Equally good
incomplete octets resonance structures

Lewis Acids and Bases

A Lewis acid is defined as an electron acceptor. They are species which are at least one
electron pair short of a filled outer shell configuration (either octet or duet), because of this they
are very reactive toward electron sources. Typically, a Lewis acid is a cation , (e.g. H+, Li+,
CH3+) or a metal atom in a salt. Neutral compounds of Boron and Aluminum (i.e. BH3, AlCl 3)
are also Lewis Acids due to the lack of an octet around both B and Al

A Lewis base is defined as an electron donor. They are species that react with Lewis acids by
supplying an electron pair. A typical Lewis base is an anion (e.g. OH-) or a neutral heteroatom
with at least one pair of non-bonding electrons (e.g. :NH3).

A Lewis acid must have available a low energy empty orbital to accept an electron
pair from the Lewis base.
 empty orbital
F
F + F B F F B F
F F

Flouride anion Boron triflouride Tetrafluoroborate anion

Lewis base Lewis acid

Reaction of Lewis Acid with a Lewis Base

Ionic Bonds and Electronegativity

ELECTRONEGATIVITY, Eneg, is a measure of an atoms ability to attract to itself the

shared electrons in a covalent bond. Electronegative elements need more electron density near
them. Electronegativity increases as you move to the right across a row in the periodic table
and decreases as you proceed down a column. Thus the elements at the top right of the periodic
table (i.e. F, O and Cl) have the greatest electronegativity, whereas the elements in the lower
left corner (i.e. Fr, Cs and Ra) have the lowest electronegativity. The American chemist Linus
Pauling developed a convenient measure of electronegativity called the Pauling Electro-
negativity Scale, in which the values range from 0.7 (lowest) for Fr to 4.0 (highest) for F.

ELECTRONEGATIVETY VALUES
H
2.1

Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0

Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0

K Ca Sc Ge As Se Br
0.8 1.0 1.3 1.8 2.0 2.4 2.8

Rb Sr Y Sn Sb Te I
0.8 1.0 1.2 1.8 1.9 2.1 2.5

Cs Ba La-Lu Pb Bi Po At
0.7 0.9 1.0-1.2 1.9 1.9 2.0 2.2

The larger the difference in electronegativity between two bonded atoms, the more ionic
character of the bond. Paulings equation for calculating ionic character: IC = 1 e .25E . Solving
2

the this equation for Eneg = 2, we get an ionic character of 63%. A difference in ionic
character of 2 is said to be an approximate threshold for ionic properties of a bond. A plot of
Paulings relationship is shown below

Pauling's Relationship for

Percent Ionic Character of Bonds as a
100.00
Function of Eneg
90.00
80.00
70.00
60.00
50.00
40.00
30.00
20.00
10.00
0.00
0 0.5 1 1.5 2 2.5 3 3.5
Difference in Electronegativity, Eneg

Like most things in nature there are "gray" areas between the ionic and covalent bond. A
POLAR COVALENT BOND is a covalent bond between two atoms of differing
electronegativity. We can predict the nature of a chemical bond by using the difference in
Pauling Electronegativities, ( E.Neg.).
There is a convient rule of thumb for using the electronegativity difference between two bonded
atoms to predict whether the bond will be ionic, covalent or polar-covalent:

Eneg = 0 The bond is completely covalent

0 < Eneg < 2.0 The bond is polar-covalent
Eneg > 2.0 The bond is considere to be ionic.
If the two bonded atoms are the same element (i.e. H2 or Cl2) then their electronegativities are
the same and Eneg = 0. The bond is totally covalent. If the difference in electronegativities is
between zero and two, for example the C-Cl bond has a Eneg = 0.5, the bond is polar-
covalent. A Li-F bond, which has a Eneg = 3.0, is considered to be essentially ionic.
 Practice Problems for Chapter 8
1. Draw the Lewis structures for each of the molecules below. Show resonance structures
where this is appropriate. On each Lewis/resonance structure show the formal charges.

a. PO33

b. PO4-3

b. NO2

2. Show the resonance hybrid structure for Question 1(b) above.

3. Circle those of the following compounds that are Lewis acids?

AlH3 H+ NaH NH3 HCl BF3

4. On the line below each compound classify each bond as ionic, covalent, or mixed using the
attached table of electronegativities.
AlI BrCl BF CaCl MgCl KS

_______ ________ _______ _______ ________ ______

5. Calculate the lattice enthalpy for KBr. Various thermodynamic properties are listed below
Standard State conditions 25C and 1.0 atm
Molar mass of Br2.160 g/mole
Boiling point of Br2(l)..59C
Specific Heat capacity for Br2 = 0.473 J g-1 K-1
Heat of vaporization for Br2(l) =15.4 kJ/mol
Bond Dissociation Energy (D) for Br2(g) = +199.6 kJ/mole
Electron affinity for Br(g) = -325 kJ/mol
Enthalpy of formation for KBr(s) = 393.80 kJ/mol
Ionization energy for K(g) = +418 kJ/mol
Enthalpy of atomization for K(s) = 89.24 kJ/mol