8.4 Bond Polarity and Electronegativity.

The concept of
electronegativity was
developed by Linus
Pauling. Electronegativity
is the ability of an element
to attract electrons to itself
in a molecule.
Electronegativity increases
across the periodic table
and is at a maximum in the
top right hand corner at
fluorine and is at a
minimum at the bottom left
hand corner at !esium.
Linus Carl Pauling
(1901-1994)

ELE!T"#$E%&T'('T)
Pauling originally developed the concept from the fact
that for ionic compounds the bond energies were
much larger for e.g. *+ than expected from the
average of the energies for the related homonuclear
diatomics in this case *
,
and +
,
. The more the
observed energy of bond formation exceeded the
average of the energies of the two related homo-
nuclear diatomics the greater the electronegativity.
Covalent electron Polar covalent Ionic one atom
Density spread equally one atom has more has attracted most of
Over both atoms electron density the electron density
e-density
high
e-density
low
e-density
spread
equally

Electronegativities Li to +
#n the next slide we have a table of
electronegativities for elements in the periodic table.
#ne sees that + .E$ / 4.01 is the most
electronegative element while !s is the least
electronegative .E$ / 0.21 The electronegativites
increase across the periodic table from Li .E$ / 3.01
to Li by 0.4 per element so that we have5
Li Be B ! $ # +
E$5 3.0 3.4 ,.0 ,.4 6.0 6.4 4.0

Electronegativities of the Elements
F with ! " #$% is
most electronegative
element
Cs &! " %$'( is least
electronegative
element
)u is at the pea* of
an island of electronegativity+
and is most electronegative metal

Electronegativities of some main group
elements5
*
,.3
Li Be B ! $ # +
3.0 3.4 ,.0 ,.4 6.0 6.4 4.0
$a 7g &l 8i P 8 !l
0.9 3., 3.4 3.8 ,.3 ,.4 6.0
: !a %a %e &s 8e Br
0.8 3.0 3.; 3.8 ,.0 ,.4 ,.8
"b 8r 'n 8n 8b Te '
0.8 3.0 3.2 3.8 3.9 ,.3 ,.4

Electronegativity and bonding5
lectronegativity tells us what *ind of bonding we have+ i$e$ whether
it is ionic or covalent$ ,he greater the difference in ! between the
two elements forming the bond+ the more ionic is the bond$ ,ypical
ranges for ! differences are-
! difference bonding type .ample ! difference
range
//////////////////////////////////////////////////////////////////////////////////
0 1$% Ionic 2iF #$%-3$% " 4$%
%$5-1$% polar covalent 6F #$%-1$3 " 3$7
8%$5 covalent F-F #$%-#$% " %$%
covalent C-6 1$5-1$3 " %$#
covalent 2i-2i 3$%-3$% " %$%
covalent )u-C 1$5-1$# " %$3

//////////////////////////////////////////////////////////////////////////////////

"elativistic effects.
#ne notes that electronegativity .E$1 is at a maximum at + and
a minimum at !s and increases from left to right and from
bottom to top in the periodic table. &n important exception is
the <island= of high E$ centered on &u. This high E$ is due to
relativistic effects ."E1. The core electrons in heavy atoms such
as &u are moving near the speed of light and this alters the
energies of the orbitals in the element. This is because the 3s
electrons in an &u atom are circling a nucleus with a charge of
>29 and so they must move very rapidly. The effect that this
has is that the energies of the s electrons in the &u atom are all
much lower than they would be in the absence of "E. This
lowering of energies even of the valence electrons in the ;s
orbital of &u leads to greater E$. The closer an element is to
&u in the periodic table the greater its E$.

"elativistic effects5
"elativistic effects arise because the inner core
electrons of very heavy elements are traveling at a
significant fraction of the speed of light. This
increases their mass according to the familiar
e?uation5
m / m
o
@.3 - .v@c11
3@,
.m / observed mass of electron m
o
/ mass of electron at rest v
is the velocity of the electron and c is the speed of light1
8ee5 $. :oltsoyannis A!8 Balton Trans 3992 3.

ver wondered at the colors of the group 39 elements+ Cu+ )g+
and )u: Cu is ;gold< colored+ then )g is not+ then )u is gold-colored$
=hy the discontinuity: ,he answer is that the color gap between the
5d and >s levels in )u metal is lowered by ?+ and so this electronic
transition occurs in the visible giving )u metal its gold color$

The chemistry of &u and surrounding
elements and the role of "E.
,he elements near )u in the periodic table all have high !+ as
shown below &gold color " ! 0 1$%( -
Fe Co !i Cu @n Aa Ae
!- 3$B 3$7 3$7 3$7 3$> 3$> 3$B
?u ?h Pd )g Cd In Cn
!- 1$1 1$1 1$1 1$3 3$' 3$' 3$B
Os Ir Pt )u 6g ,l Pb
!- 1$1 1$1 1$1 1$5 1$3 1$% 3$7
,he metals with ! 0 1$% have special chemistry where they can
form stable covalent bonds to carbon+ for e.ample+ and have
chemistry that is much more covalent than found for other less
electronegative metals$

The remarCable chemistry of the metallic
elements with E$ D ,.0
lements such as Pt+ )g+ )u+ and 6g are e.tremely
covalent in their bonding$ ,hus+ they form stable
comple.es with bonds to carbon atoms+ and other
elements with ! values of about 1-1$5$ .amples are
D)u&C!(
1
E
-
and D6g&C!(
1
E &C!
-
" cyanide( or D)u&C6
4
(
1
E
-

and D6g&C6
4
(
1
E$
6g
Ctructure of
D6g&C6
4
(
1
E

The inert pair5
,he elements after gold in the periodic table have as
their most stable o.idation state one which is 1 less than
the group valency$ ,hus+ Pb has as its most stable
o.idation state the Pb&II( state+ although Pb is in group #$
,his is referred to as the ;inert pair<+ and is thought to be
due to increased electronegativity caused by relativisitic
effects$ ,he ;inert pair< of electrons is usually
stereochemically active+ as are the lone pairs on
molecules such as ammonia+ as e.pected from FCP?-
Pb
lone pair
Cl
Ctructure of
DPbCl
4
E
-

,he lead-acid battery wor*s on the greater
stability of Pb&II( than Pb&IF( plus Pb&%(
,he reaction at the anode involves o.idation of Pb to
PbCO
#
&s( and at the cathode reduction of PbO
1
to PbCO
#
&s($
anode &Pb metal(
positive
cathode &PbO
1
(
&negative(
electrolyte "
dilute 6
1
CO
#
cathode
&PbO
1
(
anode
&Pb metal(
Pb&IF( G Pb&%( H 1 Pb&II(
vent
casing
cell divider
cell
connectors
vent caps