Chapter 9

Chemical
Bonding I
Basic Concepts

Lewis Dot Symbols

Consist of the symbols of an
element & 1 dot for each valence e
in an atom of that element.
To keep track of valence e in
chemical rxns
Elements in same group same #
of valence e (same with group
number)

Lewis Dot Symbols

The Ionic Bond

Electrostatic force that holds ions
together in an ionic cpd
Btwn metal & nonmetal
e from metal transferred to non
metal
Metal cation
Nonmetal anion
Example (Lewis e dot & e
configuration): Na & Cl, Ba & H

Lattice energy of ionic cpds

Energy required to completely
separate 1 mole of solid ionic cpd to
gaseous ions
Cannot be measured directly
Use Coulombs Law to calculate if
structure & composition of ionic cpd is
known
Potential energy (E) btwn 2 ions is
indirectly proportional to the product of
their charges and inversely proportional
to distance of separation btwn them

Coulombs Law

E is ve; charge for F is ve

Formation of ionic bond is
exothermic energy must be
supplied to reverse the process
Lattice E of LiF is +ve = bonded
pair of Li+ & F- ions is more stable
than separate Li+ & F-

Born-Haber cycle
to indirectly determine lattice
energy by assuming formation of
ionic cpd has a series of steps
Relates lattice energies of ionic
cpds to ionization energies,
electron affinities, & other atomic &
molecular properties
Based on Hesss Law

Born-Haber cycle (LiF)

Standard enthalpy of formation of
LiF is -594.1 kJ/mol
Li(s) + F2(g) LiF(s)
Sum of enthalpy changes for all
steps required to separate LiF ion
gaseous ions = -594.1 kJ/mol

Steps
1. Convert Li(s) to Li(g)
Li(s) Li(g); H1 = 155.2 kJ/mol
2. Dissociate F2(g) to 2F(g)
F2(g) 2F(g); Ha = 150.6
kJ/mol
F2(g) F(g); H2 = 75.3
kJ/mol
3. Ionize Li(g)
Li(g) Li+(g) + e; H3 = 520

Steps
4. Add 1 mol e to 1 mol F(g)
F(g) + e F-(g); H4 = -328
kJ/mol
5. Combine 1 mol Li+(g) and 1 mole
F-(g) to form solid LiF(s)
Li+(g) + F-(g) LiF(s); H5 = ?
The reverse of step 5 = lattice
energy of LiF

Born-Haber cycle

Using Hesss Law to calculate

1
2
3
4
5

Li(s) Li(g)
F2(g) F(g)
Li(g) Li+(g) + e
F(g) + e F-(g)
Li+(g) + F-(g) LiF(s)
Li(s) + F2(g) LiF(s)

155.2
75.3
520
-328
?
-594.1

Born-Haber cycle
The greater the lattice energy, the
more stable the ionic cpd
Rough correlation btwn lattice
energy & mp
Larger lattice energy more stable
ions more strongly held together
Requires more heat to melt the solid

Lattice energy & formulas of

ionic cpds
Lattice energy - a measure of
stability of ionic cpds.
Ionisation of elements rapidly
when e are removed one by one
Mg
1st ionisation energy > 2nd ionisation
energy
Mg2+ has noble gas conf very
stable

 But stability gained because lattice

energy for formation of MgCl2 is
higher than 2nd ionisation energy of
Mg

NaCl
Energy released to form NaCl too
small compared to energy absorbed
to form Na2+

O2 High lattice energy for formation of

Na2O or MgO

The Covalent Bond

Sharing of valence e btwn 2 atoms
Represented by a line
Each e is attracted to nuclei of
both atoms
Lewis structure shared e pairs
shown a s lines or pairs of dots
btwn 2 atoms & lone pairs pair of
dots on individual atom
Example (Lewis dot) H2, F2, H2O

The Covalent Bond

F2, H2O octet rule an atom
other than H form bonds until
surrounded by 8e.
Works for 2nd period elements

Type of cov bonds

Single atoms held by 1 e pair
Multiple 2 atoms share 2 or more
pairs of e
Example: C2H4, N2

Comparison of properties of
cov & ionic cpds
Attractive force in cov cpds
force holding atoms together
Force btwn molecules (intermolecular
force)

Molecules of a covalent cpds are

held weakly
Gases, iquid, low mp solids

Comparison of properties of
cov & ionic cpds
Electrostatic force btwn ionic cpds
strong
Solid at room T & high mp
Soluble in H2O & aqueous soln
conducts electricity
Molten conduct electricity

Cov cpds
insoluble & nonelectrolytes
Molten do not conduct electricity

Electronegativity
Polar (covalent) bond = e spend
more time being near to 1 atom
compared to the other
Property that helps to identify polar
bond electronegativity = ability of
an atom to attract more e to itself
in a chemical bond
Electroneg related to e affinity &
ionisation energy

Electronegativity
Relative concept can only be
measured in relative to
electronegativity of another atom
Atoms of elements with very diff
electroneg tend to form ionic bond
Atoms of same element that forms
a bond purely covalent

Electronegativity

Electronegativity
Ionic bond electronegativity diff
btwn 2 bonding atoms is 2.0 or
more
Percent ionic character directly
related to diff in electroneg (Fig
9.7)
Electron affinity isolated atoms
attraction for an additional e
Electroneg in a chemical bond

Practice exercise
Which of the following bond is
covalent, polar covalent and ionic?
Bond in CsCl
Bond in H2S
NN bond in H2NNH2

Electroneg & oxidation number

Oxn number concept
Refers to num of chgs an atom would
have if e were transferred completely
to the other more electroneg atom
N in NH2, O in H2O2

Writing Lewis structures

Basic steps
Write skeletal structure of cpd
Least electroneg center
H, F terminal

Count total num of e present

Polyatomic ions, add num of ve chg
to the total. (SO42- - 2 more)
Cations subtract the num of +ve
chg

Writing Lewis structures

Draw single covalent bond btwn
central atom & surrounding atoms
Valence shell for H is full with only 2 e
e of center & surroundings must be
shown as lone pairs if they are not
involved in bonding

If center atom has less than 8 e, try

add = or bond using lone pairs fr
surrounding atoms (CONS)

Practice exercise
Write Lewis structure for CS2,
HCOOH, NO2-

Formal Charge & Lewis

structure
Formal chg = electrical chg diff
btwn valence e in an isolated
atom& the num of e assigned to the
atom in Lewis structure
Method:
All atomss nonbonding e are
assigned to the atom
Break bonds btwn the atom & the
other atom & assign of the bonding
e to the atom

Formal Charge & Lewis

structure (O3)
O=O-O
Valence e
6 6 6
E assigned to atom
6 5 7
___________________________
Difference (formal chg) 0 +1 -1
So formal chg:

Formal chg & Lewis structure

Helpful rules
Sum of the chgs must become 0
molecules are electrically neutral sp
Cations sum of formal chgs equal
to +ve chg
Anions sum of formal chgs equal
ve chg

Formal chg & Lewis structure

Formal chg help keep track of
valence e
Get qualitative picture of chg distr
in molec
Not complete transfer of e
O3, experimental studies prove
that central O has partial +ve chg
& end O has partial ve chg.

Practice exercise
Write formal chg for NO-

Formal chg & Lewis structure

Molecules can hv more than 1
acceptable Lewis structure
The most acceptable one can be
deduced using formal chg
A Lewis structure with 0 formal chg is
more preferable
Lewis structures with smaller formal
chg more acceptable
Formal chgs on more electroneg
atoms are more acceptable

The concept of resonance

O3 double bond can be put on
either side of the molecule
But bond lengths btwn O atoms
equal (= bond shd be shorter than
single)
So both structures can be used to
represent the molecule
O

The concept of resonance

The 2 structures are called
resonance structures
Resonance structure 1 of 2 or
more Lewis structures for a
molecule that cannot be presented
accurately by only one Lewis struct
Actual molecule has own unique
structure
Resonance to address
limitations to the bonding model

The concept of resonance

Other examples
CO32 Benzene (C6H6)

The positions of e can be

rearranged in diff resonance
structures

Exceptions to the octet rule

Recall octet rule applies to
period 2 elements
Incomplete octet - # of e
surrounding central atom < 8,
valence e less than 4e
BeH2, BF3
F
F

B
F

F
F

B
F

B
F

Exceptions to the octet rule

BF3 readily react with NH3
F
F

B
F

N
H

B
F

H
-

N
H

B-N bond diff fr covalent bonds

discussed so far both e are
provided by N

Odd electron molecules

NO & NO2
Odd-e molecules sometimes
called radicals
Radicals highly reactive
Unpaired e forms cov bond with
another unpaired e of another
molecule

The expanded octet

More than 8 e surround central
atom
Atoms of element in 3 period &
beyond
Example: SF6
F
F

F
S

F
F

Bond enthalpy
Measure the stability of molecule
Enthalpy change required to break
a particular bond in 1 mole of
gaseous molecules
Table 9.4
Polyatomic molecules average
bond enthalpy
Triple bond > double > single

Use of bond enthalpies in

thermochemistry
Predict approximate enthalpy of rxn
using avg bond enthalpies
H = BE(reactants) - BE(products)
= total energy input total energy
released
H = -ve = exo, +ve = endo
Diatomic molecules accurately known
Polyatomic gives approximate results

Practice exercise
For the rxn; H2(g) + C2H4(g)
C2H6(g)
Estimate the enthalpy of rxn, using
bond enthalpy values in Table 9.4
Calculate the enthalpy of reaction,
using std enthalpies of formation.
(Hf (H2) = 0, Hf (C2H4) = 52.3,
Hf (C2H6) = -84.7)
Hrxn = nHf (products) - mHf
(reactants)

END OF CHAPTER 9