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Inorganic Chemistry 1

CHEMF214

Instructor-in-charge
Inamur R. Laskar

Electronegativity

Van Arkel-Ketelaar triangle


What is Ketelaars triangle??
A triangle based on the difference in electronegativities of the
elements in a binary compound and their average electronegativity
Utility of Ketelaars triangle.
Can be used to classify a wide range of compounds of different
kinds

A Ketelaar triangle showing how a plot of


average electronegativity against
electronegativity difference can be used to
classify the bond type for binary compounds

Van Arkel-Ketelaar triangle: Some


Problems
For MgO, = 3.44 1.31 = 2.13 and mean = 2.38. These
values place MgO in the ionic region of the triangle
By contrast for SiO2, = 0.68 and mean = 2.24. What is the
bonding character of silica

Topics to be covered
Robert S. Mulliken
(1896-1986); Noble prize in 1966
(for his fundamental work concerning
chemical bonds and the electronic
structure of molecules by the molecular
orbital method)

Basis/background for framing Mullikens electronegativity (EN)


Mullikens EN equation (from Paulings EN)

Electronegativity vs Ionization Energy


and Electron affinity
The neutral atoms of different elements have differing abilities to gain or
lose electrons. These properties are known as the electron affinity and
ionization energy of a given element, and they can be quantitated
experimentally.
Electron affinity of an element is a measure of the energy released (or
gained, in some cases) when one electron is added to an atom of that
element. Ionization energy is the energy needed to remove an electron
from an atom of that element.
Atoms that attract electrons more strongly have relatively higher
ionization energy and electron affinity, and they tend to form monatomic
ions with a negative charge. They tend to be the atoms of nonmetals.
Atoms that attract electrons more weakly have lower ionization energy
and electron affinity, and they form ions with a positive charge. They tend
to be the atoms of metallic elements.

Mulliken-Jaffes Electronegativity
Mullikens EN equation (from Paulings EN)
M = 0.336[IEv + EAv/2 0.615] (where the energies are in electron
volts)

Total Energy (IEs + EAs) Curves for Different


Elements at various Oxidation States

Plotting of ionization
energies electron
affinities results a
smooth curve and the
function can be described
accurately by the
following
quadratic formula,
E = q + q2 ; E is the
total energy of the ion
(IE or EA
What are the observations??

Jaffes Definition of Mullikens


Electronegativity
Mullikens definition of EN is equal to the slope of the curve as
it passes through the origin
It indicates that an atom will be highly electronegative if it
releases much energy (energy curve will be steep) as it
acquires electron density
Another atom will be less electronegative because its curve is
less steep and when combined with the more EN atom, it
does not cost as much energy climbing its own energy curve
Hence for the case of ClF, it will form Cl(+)F(-) not the other
way
(follow the energy curve for Cl and F at the next page)

Relationship between Mulliken and Jaffe


and Merits of Mulliken-Jaffes EN
IEv + EAv = 2,

so Mulliken EN =

Mulliken-Jaffe EN is able to determine at hybridized state of


the element

Capable of treating EN of partially charged atoms


= dE/d = a + b
Significance of a
Significance of b, b = d2E/d2 = d/d = IEv Eav
b = 1/K
Why F has only a limited ability to donate or absorb electron
density before its EN changes too much??