CHAPTER 9

IONIC AND COVALENT BONDING

I. INTRODUCTION

A) Chapters 7 and 8 dealt with isolated atoms

and their electronic properties.
B) Many chemists are interested in molecules
and compounds.
C) All the tremendous variety of materials
found in our physical world may be
interpreted and understood as a combination
of about 100 elements.
D) Chemical Abstracts registers compounds
and gives each one a number - over 7 million
have been registered and there are 17 million
names.
E) What kind of models do we have for these
compounds???

F) What is the glue that holds species

together?
G) A chemical bond is the glue which holds
atoms together to make more than one atom
molecules and ionic substances.
H) Two classes of chemical bonds have been
mentioned throughout this semester:
1) Ionic bond - formed by the attraction
between positive and negative ions - it is
electrostatic in nature.
2) Covalent bond - a chemical bond formed
by the sharing of a pair of electrons between
atoms.
I) KEY POINT When atoms interact to form
a chemical bond, only their outermost
regions are in contact.
For this reason, when we study chemical
bonding we are interested in the outermost
electrons of an atom primarily; its valence
electrons.

J) Elements with similar electron

configurations (THE SAME NUMBER OF
VALENCE ELECTRONS) behave alike
chemically, a family, a group, a column.
II. LEWIS (DOT) SYMBOLS FOR THE
ELEMENTS
A) A Lewis dot structure for an atom consists
of the symbol for the element and one dot for
each valence electron. It is used for the s and
p block elements, the representative elements.
C) Elements in the same column, the A
columns or columns 1 and 2 and columns 13 -
18, have similar dot configurations. (We don't
use this symbolism for the transition elements
and the inner transition elements the actinides
and the lanthanides). We use it only with the
representative elements.
III. THE IONIC BOND
A) Ionic compounds are held together, for the
most part, by strong electrostatic forces
between oppositely charged species.
B) A simple model, which is not the whole
story as with most ideas in this course, is that
ions are formed through the transfer of
electrons from one atom to another.

C) Electrons are given by metal atoms to

nonmetal atoms. The metal atom forms a
____________, the nonmetal a________. For
the representative metals and nonmetals this
involves the formation a species with a noble
gas electron configuration. What is that?
D) Na [Ne]3s1 + Cl [Ne] 3s23p5  Na+[Ne] + Cl- [Ar]

E) Cation formation, the formation of

a___________, involves the removal of 1 or
more electrons from the highest occupied n
shell.
F) Anion formation, the formation of a
__________, involves the addition of
_____________________ .
G) IONIC RADIUS
1) The radius of a cation (+ ion) is always
_____ than the covalent radius of the parent
atom. For example: 20Ca [Ar] 4s2 197 pm.
It has 20 protons in the nucleus, 18 shielding
electrons, and 2 in the outermost shell giving
an effective nuclear charge of _______ .
For the Ca2+ ion [Ar] or([Ne] 3s23p6) 99 pm is
the radius. There are still 20 protons in the
nucleus, but now there are only 10 shielding
electrons giving an effective nuclear charge of
+10.
An increase in the ENC gives a greater
attraction on the remaining electrons, making
the species ________ .

2) The radius of an anion is always ________

than the covalent radius of the parent atom.
For Example: F 1s22s22p5 72 pm, 9 protons 2
electrons shielding and 7 valence electrons.
for F- 1s22s22p6 136 pm still 9 protons, and 2
shielding, but now there are 8 electrons in the
outermost shell “seeing” 7 positive charges in
the center.
There is a decrease in the effective nuclear
charge "felt" by each outermost electron,
7p/7e vs 7p/8e and a greater repulsive force
among the electrons accounts for this increase
in size trend. Why greater repulsive force?
Arrange the following in order of increasing
size:
O2- Na+ Mg2+ F- Ne Al3+ N3-
a) What is special about this series of ions and
atom?
They all have the same number of electrons. It
is an isoelectronic series.
b) We put them in the order of their increasing
atomic number, the order as they appear on
the periodic chart:

the greater the nuclear charge exerting the

attraction on the same number of electrons
equals a smaller size:
 The order of increasing size would be:
_____________________________________ .
H) General Statements about ionic
compounds:
1) Ionic compounds are electrically neutral -
the number of positive charges equals the
number of negative charges.
2) Ionic compounds have formulas which are
empirical formulas. They contain no molecules.
3) The glue which holds the ions together is a
strong electrical attraction between ions of
opposite charge.
IV. COVALENT BONDS
A) Covalent bonds are formed when 2 atoms
share 1 or more pairs of electrons achieving
the lowest possible energy.
B) Atoms which form covalent bonds are very
similar in their tendency to gain or lose
electron. In general, covalent bonds are
formed between nonmetal atoms.
C) Lewis structures, which are very
elementary models of molecules, work well for
lots of molecules especially organic molecules.
D) A Lewis Structure (an electron dot
formula) is a representation of covalent
bonding using Lewis dot symbols in which
shared electron pairs are shown as a pair of
dots or a line between two atoms. The lone
pairs of electrons are shown as pairs of dots on
individual atoms.
E) Many molecules obey what is known as the
octet rule. That is, when atoms form covalent
bonds there is a tendency to share enough
electrons so that each atom is surrounded by
8 electrons. (Our magic number)
1) Exceptions - fewer than 8 are required for
H, He, Li, Be, and B. H - 2; He - 2; Li is usually
ionic where it loses 1 electron, Be when
covalent shares 4, and B can sometimes share
6.
2) More than 8 electrons are shared by some
atoms especially those atoms beyond the
second row which have d orbitals available for
bonding. More than 4 positions are available
for bonding.
V. LEWIS STRUCTURE BUILDING -
GAME WITH RULES
A) You must determine enough of the
structure so that you know which atoms are
bonded to which atoms.
This comes from your knowledge of what
follows or if there are exceptions then I will
have to tell you. You will have to make
educated guesses based on :
1) H and F can only form ONE bond,
therefore they cannot be in the middle of a
molecule, they must be on the end of a
molecule. H2O must be:

not H-H-O

BF3 must be:

not B-F-F-F
2) The Central atom of a molecule or
polyatomic ion (atoms held together with
covalent bonds with extra electrons provided
by metal atoms being converted into positive
ions) is usually the one that there is only one
in the formula.
3) It is very unusual for oxygen atoms to bond
together. DON'T DRAW S-O-O-O-O for SO42-
Do draw:

4) In carbon compounds, the compounds of

organic chemistry, the carbon atoms can bond
to carbon atoms and each carbon atom
generally has 4 bonds altogether.
In organic compounds we find C atoms
forming 2 bonds with O atoms, 1 bond with H
atoms and atoms of the halogens, 3 bonds with
N atoms, 1, 2, or 3 bonds with other C atoms.
B) Use the Periodic Table to determine the
total number of electrons available for
distribution among the atoms in a molecule.
1) Example - CH4
C is in Group 4 = 4 e
H is in Group 1 X 4 = 4e.
4e + 4e = 8e
Put 8 dots around the C in the middle and
attach an H to the C with each pair of dots.
This will give each C 8 electrons to satisfy the
octet rule, and each H 2 electrons which will
satisfy it. This gives the following structure
when the lines are substituted for the dots.
2) for SO42- we obtain the following:
S and O are both in group 6 so we multiply 5
atoms times 6e/atom to obtain 30 electrons + 2
for the -2 charge (2 extra electrons) = 32e. We
distribute them so that the structure is:
For atoms which require 8e, find the number
of electrons shared between atoms by taking 8
times the number of atoms in the molecule
requiring 8e and subtract the number
available from it to find the number of bonds.
CF4
C contributes 4 electrons, the 4 F's each
contribute 7, making available 28 + 4 = 32
electrons are available.
There are 5 atoms in the molecule which each
require 8 electrons to complete their octet
which means 40 electrons are required.
Needed minus available = shared 40 - 32 = 8
which are shared, which means 4 bonds are
needed since there are 2 electrons per bond.
We put C in the middle, allowing each F to
bond with it. This uses 8 electrons. There are
then 32 - 8 = 24 to place around the 4 F's. This
allows 6 e's per F which will complete the
octet around each F.
D) For some molecules the above calculation
leads to a situation where electrons are in
short supply. When this occurs, multiple
bonds are required.
For example, N2.
Each N contributes 5 electrons making a total
of 10 available.
Each N requires 8 electrons making total of 16
required.
16 - 10 = 6 divided by 2 electrons per bond = 3
bonds required. we must put the three bonds
between the two nitrogen atoms as follows:
For SO2, we obtain the following:
The S and the O are in the some column of the
periodic chart so they each contribute_______.
Each S and O require 8 electrons for a total of
_____________.
24 electrons needed with 18 available leaving 6
electrons to be shared divided by 2 giving 3
bonds. Where to put them?
S must be in the middle so the following is a
possibility:

BUT WHAT ABOUT THE FOLLOWING:

This would indicate that one bond would be
shorter than the other since double bonds are
shorter than the single bonds. The
experimental evidence is that both bonds are
identical.
According to the theory then, one of the
bonding pairs in sulfur dioxide is spread over a
number of atoms rather than localized
between 2 atoms. This is called delocalized
bonding and in the Lewis concept both
structures must be shown.
A single dot formula cannot properly describe
delocalized bonding. Instead a resonance
description is used.

For the CO32- ion we obtain the following:

We obtain three required resonance
structures as follows:
VI. SOME BOND PROPERTIES
A) Polarity

B) Bond Strength
C) Bond Length
VII. Bond Polarity
A) Bond Polarity is a useful concept for
describing entire molecules as well as
individual bonds.
B) H2 is the simplest molecule - a nonpolar
molecule since the center of positive charge
coincides with the center of negative charge.
H:H
C) Covalent bonds between two different
atoms are generally polar H-F H-Cl
D) Electrons are not shared equally between
the bonded atoms. A polar covalent bond is a
covalent bond in which the electrons spend
more time in the vicinity of one of the atoms
than another.
E) H-Cl The two bonding electrons spend
more time in the vicinity of the Cl atom than
the H atom.
The arrow indicates that HCl possesses a
dipole moment in the direction of the Cl atom,
the partially negatively charged one.
You have a polar molecule when the _____
and ______ charges do not _____________ .
F) We need a criterion by which to predict
whether a bond is nonpolar covalent, polar
covalent, or ionic.

G) We have to think of bonding type as a

continuum from normal (nonpolar) covalent
to polar covalent to ionic.
H) the criterion we will use is the difference
in electronegativity.
1) What is electronegativity?
2) It is a measure of how strongly an atom
attracts the bonding electrons in a chemical
bond. The higher the electronegativity, the
stronger an atom's attraction for bonding
electrons.
3) We will use the Pauling Scale of
Electronegativities - there are other scales
known and used.
4) Electronegativity increases______________.
We will ignore the noble gases since their
compounds are of recent origin.
5) Electronegativity decreases _____________ .
6) Of the commonly occurring elements, this
makes _________ the most electronegative and
______________the least..
7) Atoms of the same electronegativity joined
by a covalent bond give an electronegativity
difference of zero - i.e. H2 2.1 - 2.1 = 0. This
indicates a normal nonpolar covalent bond.
8) Electronegativity differences greater than
zero and less than two usually give a polar
covalent bond. (Some books use up to a 0.5
difference as still being nonpolar because C-
H bonds are generally considered nonpolar.)
9) Electronegativity differences of 2 or greater
are associated with ionic bonds. Remember
this is an attempt at classification and the real
world just doesn't obey these manmade rules,
so there will be exceptions.
10) EXAMPLES
VIII. FORMAL CHARGE AND LEWIS
FORMULAS
A) The formal charge of an atom in a Lewis
formula is the hypothetical charge you obtain
by assuming that bonding electrons are
equally shared between bonded atoms and
that the electrons of each lone pair belong
completely to one atom.
B) Formal charge = # of electrons in the
valence shell minus the number of bonds to
the atom minus number of unshared electrons
surrounding atom.
C) Two rules that are useful in writing Lewis
formulas using the concept of Formal Charge
are:
1. When several Lewis Structures can be
written for a given compound, the one which
contains the smallest formal charges is
preferred.
2. When two proposed Lewis formulas for a
molecule have the same magnitudes of formal
charges, choose the one with the negative
formal charge on the more electronegative
atom.
3. Example:
H2SO4

The formal charge on S is ________.

The formal charge on the O's connected to the
S and H is ___________.
The formal charge on the O's connected to
the S only is _____________.
Note that the sum of the formal charges is
zero as it should be for a neutral molecule.
It should also be noted that a structure for
H2SO4 can be written that has zero formal
charges. This is accomplished by putting
double bonds between the S and O atoms
which do not have H's attached to them.
IX. BOND LENGTH
A) Bond length is the distance between the
nuclei in a bond. These are determined by X-
ray diffraction. This is always an average
distance, because atoms are always vibrating
with respect to each other, so there is really
no fixed distance between any two nuclei.
B) Bond length decreases from single to
double to triple bonds. C-C (154 pm) C=C
(133 pm) Triple bonded carbon atoms (120
pm).
X. BOND STRENGTH
A) Bond energy is the average enthalpy change
for the breaking of an A-B bond in a molecule
in the gas phase.
B) For example:
CH4  C(g) + 4 H(g) H = 1662kJ
Because 4 C-H bonds were broken, we obtain
an average value of the bond energy for the
C-H bond as ¼ 1662 kJ = 416 kJ. From other
molecules containing C-H bonds we obtain an
average value found in the book as 411 kJ
C) Bond energy is a measure of the strength of
a bond: the larger the B.E. the stronger the
chemical bond. C-C is weaker than C=C, and
that in turn is weaker than C triple bond C.
D) You can use a table of B.E's. to estimate
heats of reaction. The enthalpy of reaction is
approximately equal to the sum of the bond
energies for bonds broken (always
endothermic) minus the sum of the bond
energies for the bonds formed (always
exothermic - the negative of the B.E.).