Scribd Logo
Upload

Welcome to Scribd!

  • 80 views

    Electronegativity Equalization With Pauling Units

    Uploaded by

    Henrique Santos
    This document discusses electronegativity equalization and a method for calculating partial charges on atoms using Pauling electronegativity units. It presents Sanderson's principle of electronegativity equalization, which states that when elements combine chemically, their electronegativities equalize to an intermediate value within the compound. The document then derives equations that allow calculating the partial charge on each atom based on the initial and equalized Pauling electronegativities. It provides examples of applying the equations and compares the partial charges calculated by this method to other established methods.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd

    Electronegativity Equalization With Pauling Units

    Uploaded by

    Henrique Santos
    80 views2 pages
    This document discusses electronegativity equalization and a method for calculating partial charges on atoms using Pauling electronegativity units. It presents Sanderson's principle of electronegativity equalization, which states that when elements combine chemically, their electronegativities equalize to an intermediate value within the compound. The document then derives equations that allow calculating the partial charge on each atom based on the initial and equalized Pauling electronegativities. It provides examples of applying the equations and compares the partial charges calculated by this method to other established methods.

    Original Description:

    Pauling

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    This document discusses electronegativity equalization and a method for calculating partial charges on atoms using Pauling electronegativity units. It presents Sanderson's principle of electronegativity equalization, which states that when elements combine chemically, their electronegativities equalize to an intermediate value within the compound. The document then derives equations that allow calculating the partial charge on each atom based on the initial and equalized Pauling electronegativities. It provides examples of applying the equations and compares the partial charges calculated by this method to other established methods.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    80 views2 pages

    Electronegativity Equalization With Pauling Units

    Uploaded by

    Henrique Santos
    This document discusses electronegativity equalization and a method for calculating partial charges on atoms using Pauling electronegativity units. It presents Sanderson's principle of electronegativity equalization, which states that when elements combine chemically, their electronegativities equalize to an intermediate value within the compound. The document then derives equations that allow calculating the partial charge on each atom based on the initial and equalized Pauling electronegativities. It provides examples of applying the equations and compares the partial charges calculated by this method to other established methods.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 2

    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.
    588

    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"".

    (31 Hinze, J., Whitehead, M. A,, and Jsffe, H. H., J. Amor. Chom. Soe.,85,148(19631.
    I41 Huheey, J. E., J. Phys. Cham., 69,3284 (19651.
    (51 Pam, R. G.,Donnelly, R. A,, Levy, M., and Palke, W. E., J. Chem. Phys.. 68. 3801
    114711)
    ,. .-,.
    I61 Politzer,P.,snd Wcinstein,H., J Chem. Phys.,71,4218t1979).
    (7) Reed, J.L.,J. Phys Chem.,85. 148(19811.
    I81 Pritehard,H.O.,snd Skinner, H.A.,Chem. Rau.,55.745 (19551.
    (9) Pauling, L.;'The Nature of the Chemical Bond." 3rd ed., Cornell University Press,
    Ithaea,NY, 1960, Is1 pp.8b95, (bl p.88, lcl p. 98.
    (LO) Ssnderson. R. T., 'Chemical Periodicity."Reinhold, New York, 1960.
    (111 Sanderson. R T., "lnuwnieChemistry: Reinhold, NewYork, 1967, (a) p. 81,(blp.

    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).
    (I41 Skinner,H.A.,and Pritehard.H.0,TlDw FamdoySoc..49,125411953).
    I151 Hinze, J., and Jaffe,H. H.. J. Amr. Chem. Sm., 84.540 (19621.
    (161 Allrpd,A.L.,J. Inorg Nuci Cham., l7.215 (19611.
    (171 Hinze, J.,anJ Jaffe,H.H.. J . Phya..Chem.,67,1501(19631.
    (18) Evans,R. S.. and Huheey, J. E.. J Inorg. Nucl Chem.. 32.777 (19701.
    (191 Hannay, N. B.,andSmyth,C.P.,J Amer Chem. Soe.,68,171I19461.
    (201 Wilmshurst, J. K., J. Chem Phys.30.561 l1959l.
    EDUC.,29,539(19521.
    (211 Sanderson, R.T.,J.CHEM.
    (22) Ssnderson.R. T.,J. CHEM EDUC.,31.2 119541.
    (231 Sander8on.R.T..J.CHBM. EDUC.,31,238 (19541.
    (241 Sanders0n.R. T.,Inor#.Chsm.3.925 119641.
    (25) Sanderson. R. T., J. Inore. Nucl Chem., 28.1553 11966).
    (26) Sanderson,R. T.. J. CHEW E~~c.,44,516
    (19671.

    Volume 61 Number 7 July 1984

    589

    You might also like