Electronegativity Equalization with Pauling Units

Steven G. Bratsch
The University of Texas, Austin, TX 78712

A significant development in the eleetronegativity concept

has been provided by Sanderson's formulation of the Principle
of Electronegativity Equalization (1,Za): "When two or more
elements initially different in electronegativity combine
chemically, they become adjusted to the same, intermediate
electronegativity within the compound." This principle, which
has gained wide acceptance in recent years (3-7), abandons
the idea of "fixed" electronegativity (8,9) and redefines the
values in electronegativity tables as quantities characteristic
of the isolated atom before a bond is formed (3.7).
The physical and chemical properties of kbs&nces are
lareelv determined bv the partial charges on the constituent
atoms ( l 0 , I I ), and the evaluation of tKese partial charges is
an important electronegativity application. In the framework
of Sanderson's principle, i t is generally believed that the
partial charge acquired by an atom through chemical comhination is proportional to the difference between the final,
equalized electronegativity and the initial, pre-bonded electronegativity (2b,3-7,12). In order to compute the partial
charge one must know the equalized electronegativity value
and the proportionality factor.
I t is essential in the development of any partial charge
method that charge conseruation be maintained: In a polyatomic species of integral charge q , the weighted sum of all
partial charges must he equal to q
In this equation, u represents the number of atoms of a particular element in the species formula (e.g., for B F ~ - Q= 1and
YF = 4) and 6 represents the partial charges on these atoms.
Appllcatlon wlth Pauling Unlts ( 9 a )
In describing the partial charge method developed fur the
Mulliken scale (13).
. .. Huheev 141has mentioned that most elements approximately double their (Mulliken) electronega+1 whereas their
tivities as the partial charee
. a~nroaches
..
electroneystivities essentially d~sapptar(approach zero) as
the nartial charee avvroaches - 1. The Mulliken and l'aulinr
scaies are rougKly &oportional (8, 14, 151, so Huheey's ob'servation may be expressed in Pauling units as

Here, X,, is the electronegativity as equalized through Sandemon's principle, X A is the initial, pre-bonded electronegativitv ofa particular atom A, and & A is the partial charre un
A. charge ckservation (eqn.1) leads to a general expre&on
for X,,
N+9
X. = -

(3)

where N = 2(u) = the total number of atoms in the species

formula.
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Journal of Chemical Education

Two examples serve to illustrate the usage of eqns. (2) and

(3) (Pauling electronegativities from 16).
Example 1. Hydrogen Sulfide, HzS.

Example 2. Fluorosilicote Ion, SiFs2-

In example 2, the sum 6si + SF = -1.99 rather than -2.00

merely because of rounding error.
Some partial charges calculated through eqns. (2) and (3)
are given in the accompanying table, using Pauling electronegativities as redetermined by Allred (16). For comparison,
the table also lists partial charges derived by Sanderson's
method (26) (using Sanderson electronegativities (Zc)),by the
Jaffe-Huheey method (3,4) (using Mulliken electronegativities (15,171) and by the Evans-Huheey method (18). The
latter method uses Mulliken electronegativities hut employs
an energy minimization technique which attempts to account
for the loss in orbital overlap and the increase in the Madelung
potential accompanying a transfer of charge between
atoms.
Discussion
Pauling has qualitatively defined electronegativity as "the
power of an atom in a molecule to attract electrons to itself'
(96); however, in the present work Pauling electronegativities
are treated as pre-bonded, isolated-atom quantities. This
conflict may simply reflect a misconception in the Pauling
definition (Zd, 3,7, l l a , 12) and need not cast doubt upon the
interritv
.. . of the Pauline values themselves. A definition of
electronegativity more compatible with Sandenon's priuciple
lulthwrh still uualitative~is .'the tendencv to become nerutively charged'; (llb). If an atom acquires negative charge
through chemical combination its tendency to become negatively charged decreases, as does the electronegativity. The
converse is true if an atom acquires positive charge (2e).
Partial charge methods applicable to Pauling units have
generally been developed within the context of "fixed" electronegativity, expressing charge distribution in terms of
fractional ionic character (I) of individual bonds, ex., (9c, 19,

Cornparl~nsot Partial Charms

Mullikend

Species

Atom

This
Wak'

Sandersonb

vsL

Jaffe-

Evans-

Huheey'

Huheeyg

NaF

KC1
CaCI*
SrBr*

BFai
CH,
CHso-

CF,
Sill

NH3
NFs

N(CHdf
H30+

He0

OHHIS
H
F

ncl

the years he has developed an elaborate system of bond energy

calculation ( 2 , l l , 24-26). Sanderson's successful treatment
of bond energy suggests an "absolute" significance to his
partial charges (2f). However, Evans and Huheey (18)have
indicated oossible theoretical deficiencies in Sandersou's
work, examples being Sanderson's method of selection of an
"ionic blendine coefficient" and his assumotion of a linear
relationship between covalent energy and partial charge. The
oartial charges of Evans and Huheev are often ouite different
&om ~anderson'svalues (see table);but they are nevertheless
useful in calculating lmnd energies. This apparent paradox
is the result of the different chemical bonding models used and
indicates that the question of "absolute" partial charges remains unanswered.
Partial charges calculated through eqns. (2) and (3) are not
claimed to he better than previous estimates. The intent of
this oauer has merelv been to offer a simole ada~tationof
sanderion's ~ r i n c i ~of
i e~lectrone~ativit;
~ ~ u a i i z a t i oton
Pauling units. The Pauling scale is the most familiar electronegativity scale and is often the only one seen (or at least remembered) by beginning chemistry students. This new partial
charge method should find immediate use in the qualitative
understanding of chemical behavior. However, it will probably
take considerable time and effort to develop quantitative
ao~licationsof esns. ( 2 ) and (3) (note that Sanderson's bond
enkrgy method did not come about overnight).
In addition, there are situations where electronegativity
equalization does not occur:
1) When the structure of an ionic substance prevents danor-aceeptor interaction between adjacent counter-ions, for example in
IN(CH4f
.. llB(CH4-I
,, .
.. , and oerhaos in s i m ~ l eammonium and
;h&honiwn salts, hydrated salts, etc. It meille hest to vreu such
cmnpwnds ar cumplurely ionic.
21 When the maximum possible charge transfer ior a pnrciculor
atom uccurs before rlcctroneyativity equali7.ation can be achieved.
An example r+cesiumfluunhratc ( C ~ B F Itor
I , which eqns. 12) and
13, predict 6,:, = ~ 1 . 7(an
5 rmwsiilrle value). In such caseseach ion
(e.g, Csf, B F ~ - )must be treaied individually

Acknowledgment

IF

BrCl

Paullng elecwneqativnieo from t1@;Partial charges calculated via eqns. (2) and

I am grateful to the Robert A. Welch Foundation (Grant

Number Foal), and especially to Joseph J. Lagowski, for their
s u.~.n o rof
t this research.
Literature Clted

A"".

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114711)
,. .-,.
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Equation (6) (Wilmshurst's equation (20)) is interesting because eqns. (2) and (3) reduce to it in the special case of a
uni-univalent molecule (HC1, NaF, etc.).
Sanderson has correlated his partial charges with a wide
variety of chemical phenomena (IO,11,21-231, and through

(12) Ponec, R., Theoret. Chim. Acla ( B e d ) ,59,629 (1990).

(131 Mullikan. R. S.,J Chem. Phys.. 2.782 (1934).
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