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The bond-type triangle is being used increasingly in un- Recent work has focused on the rationalization of the
dergraduate textbooks to illustrate the central importance of bond triangle by using functions of electronegativity as the
electronegativity and its influence on bond type (1a, 2). It basis for determining the positions of substances within it.
has long been recognized that chemical bonds can be divided Jensen (5), Allen et al. (6), and Sproul (7) all recognized the
into three fundamental types: ionic, covalent, and metallic. essential role of electronegativity and electronegativity dif-
van Arkel’s (3) depiction of the three bond types as the verti- ference in determining the properties of substances. All of
ces of a triangle, with compounds or elements of intermedi- them concluded that the position of any binary compound
ate nature being located along the edges, was the first to in the bond triangle could be specified by two coordinates:
attract widespread attention (Figure 1A).1 Ketalaar (4) fur- electronegativity difference (∆χ) and average electronegativ-
ther developed the bond triangle by placing compounds ity (χav) (Figure 2). These authors noted that plotting a graph
within it as well as on the edges (Figure 1B). of ∆χ versus χav produces a triangular array with ionic com-
pounds (high ∆χ, moderate χav) near the top, metals (low
∆χ, low χav) near the lower left, and covalent substances (low
∆χ, high χav) near the lower right. Both Sproul and Allen
suggested that the bond triangle as defined above can be di-
A vided into covalent, ionic, and metallic regions with straight
lines as boundaries.
In the triangles devised by each of these authors (Figure
2), the vertices are occupied by Cs (metallic), F2 (covalent),
and CsF (ionic); the elements lie along the metallic–cova-
lent axis (∆χ = 0), while cesium compounds and fluorides
are found along the metallic–ionic and covalent–ionic edges,
respectively. As observed by Jensen (5), the compounds of
any element other than Cs or F lie on two diagonal lines,
parallel to the metallic–ionic and covalent–ionic edges, which
meet at the position occupied by the element itself. The left
line (with negative slope) includes compounds of the element
with elements less electronegative than itself, while the right
line (with positive slope) includes the compounds of the ele-
ment with more electronegative elements. All compounds
formed by a given pair of elements occupy the same posi-
tion.
Sproul (7b) did the most extensive work on quantifica-
tion of the bond triangle, plotting values of ∆χ versus χav for
311 binary compounds and observing excellent correlation
B between position on the graph and bond type as specified by
Wells (8). He excluded compounds whose bond type was said
by Wells to be “ambiguous or questionable”, such as “semi-
metallic” compounds. Sproul examined 15 different elec-
tronegativity scales and found that the best agreement
between position and bond type was obtained when Allen’s
spectroscopic electronegativity (9)—later called configuration
energy (10)—was used,2 only 9 of the 311 compounds be-
ing “misplaced” from their specified regions. He found that,
for his selected compounds, the triangle could be divided into
covalent, ionic, and metallic regions by straight lines, paral-
lel to the metallic–ionic and covalent–ionic edges of the tri-
angle (Figure 2 bottom). These boundaries were defined by
the equations (with χ values converted to Pauling units):
Electronegativity Difference / PU
These boundaries are not entirely satisfactory, probably 4
because some of the compounds used were inappropriate (see
below) and Wells’s specifications of bond type are inaccurate
3 I
in some cases and ambiguous in others. The covalent–ionic
borderline is just below the line that includes all compounds
2
of aluminum (χ = 9.53 eV = 1.61 PU) with elements of
higher electronegativity, while the metal–nonmetal (metal–
insulator) line lies between those that include compounds of 1 M C
phosphorus (χ = 13.3 eV = 2.25 PU) and of hydrogen (χ =
13.6 eV = 2.30 PU) with metals and metalloids. Accordingly, 0
0 1 2 3 4 5
1. No element with electronegativity greater than that of Average Electronegativity / PU
Al would exhibit cationic character in any compound,
even with fluorine; Hg, Ga, In, Tl, Sn, and Pb are cat- B 5
Electronegativity Difference / PU
ionic in some compounds.
4
2. All elements with electronegativity equal to or less than
that of Al would form only ionic compounds with el-
3
ements more electronegative than P; the amphoteric
metals Al, Be, Cd, and Zn form covalent (or interme- I
diate) compounds with many nonmetals. 2
ary and the negative slope of the metal–nonmetal boundary Table 1. Dependence of Ionic Character on χav
in Sproul’s and Allen’s representations (Figure 3B). Sproul (7d) Predominant
points out that, if ionic character were associated only with a Substance ∆χ/PU χav/PU ∆χ:χav
Bond Type
large ∆χ, there would be a horizontal line at some critical ∆χ
LiCl 1.96 1.89 1.037 Ionic
value such as the frequently cited 1.7 Pauling units (13), sepa-
rating ionic species from others.3 Furthermore, if metallic char- HF 1.89 3.25 0.582 Covalent
acter were associated only with a small χav, there would be a LiI 1.45 1.64 0.884 Ionic
vertical line at some critical χav value—perhaps between those
AlN 1.45 2.34 0.620 Intermediate
of Pb, the most electronegative metal, and Si, the least elec-
tronegative nonmetal—separating metals from nonmetals. BrF 1.50 3.44 0.436 Covalent
Although the above authors have demonstrated that bond LiBi 1.10 1.46 0.753 Metallic
type depends on both ∆χ and χav, none of them has offered
MgSe 1.13 1.86 0.608 Ionic
an explanation for the manner in which ionic–covalent or
metallic–nonmetallic character varies with both parameters. CO 1.07 3.08 0.347 Covalent
We now address these matters. We will also show that there NOte: χ values (Pauling units) from ref 19.
are gaps between the regions occupied by predominantly ionic
and predominantly covalent substances, and between metals
and nonmetals, which are occupied by substances generally Identical expressions are obtained using the methods of
regarded as being of “intermediate” nature. Bratsch (16) and von Szentpaly (17), if one makes the ap-
proximation that the charge coefficient (16) or atomic hard-
Ionic versus Covalent Bonding: Partial Charge ness (17) of an atom is equal to its electronegativity.
In Allen’s modified Lewis–Langmuir method (18), for
The dependence of ionic character on χav as well as on diatomic molecules with single bonds:
∆χ is shown in Table 1; for each group of compounds with
very similar ∆χ values, ionic character decreases as χav in- No. of
χA
creases. This variation results from the fact that partial charge, qA = Group No. − Unpaired − 2 (3a)
rather than ∆χ alone, is the critical parameter in determin- Electrons χA + χB
ing ionicity. Although the unequal distribution of charge has
its origin in ∆χ, the magnitude of the partial charge is also Thus, if neither atom has a formal charge:
dependent on χav. We will show that partial charge is in fact
2 χA χB − χ A ∆χ
closely related to the ratio ∆χ: χav. qA = 1 − = =
χ A + χB χ A + χB 2 χ av (3b)
For diatomic singly bonded molecules of general formula
AB, Wilmshurst (14) suggested that the partial charge on A According to all of these equations, the partial charges
(qA) is given by, of bonded atoms (hence ionic character of a bond) increases
χB − χ A as the ratio ∆χ: χav increases, and all compounds whose at-
qA = (1a) oms have the same partial charges will have the same ∆χ: χav
χB + χ A
ratio. Thus in a bond triangle with axes ∆χ and χav, all com-
pounds with the same degree of ionic character will lie on a
where χA and χB are the electronegativities of elements A and
straight line, passing through the origin (∆χ = χav = 0) when
B. Thus
extrapolated, with slope equal to 2q (Figure 3C). One such
∆χ line will have a slope equal to the critical q value above which
qA = (1b) compounds are predominantly ionic, and will correspond to
2 χ av
the “ionic–covalent” boundary.
At least four other more recently derived equations for In fact, for diatomic molecules with multiple bonds the
evaluating partial charge can be shown to be equivalent to partial charge is equal to the ∆χ:2χav ratio multiplied by the
eq 1b. Smith (15) used an electronegativity equilibration ap- bond order; this is recognized by Wilmshurst (14) and Allen
proach to show that, in the singly bonded molecule AB, the (18) in their articles, but the equalization-based methods (15,
partial charge on A is given by, 16) do not take bond order into account and von Szentpaly
(17) considers only singly bonded molecules. Still, the ratio
χ − χA 2 χ A χB ∆χ: χav in molecules with multiple bonds is equal to twice
qA = , where χ = (2a)
χA χ A + χB the partial charge per bond and gives a good indication of
the extent of ionic character in the bond.
thus:
Metals versus Nonmetals: Band Gap
χ 2 χ A χB 1
qA = −1 = −1 The critical parameter in determining metallic behavior
χA χ A + χB χA
is band gap (E g), since conductivity is proportional to
χB − χ A ∆χ (2b) exp(᎑Eg兾kT). Thus substances with very small band gaps are
= = metallic conductors, while those with large band gaps are in-
χA + χ B 2 χ av sulators. For the elements, it has been established (19) that
Boundaries: Well-Defined Compounds and Elements wood and Earnshaw (26) as being predominantly of one type.
A plot of ∆χ vs (χav)w (Figure 4) was constructed for these
The selection of compounds for establishing boundaries compounds; the 37 “well-defined” elements of these groups
between predominant bond types should be restricted to bi- —omitting the metalloids—were also included, to help es-
nary compounds that have been isolated and purified, have tablish the covalent–metallic boundary. All of these species
known structures, and contain only heteronuclear bonds. This are listed in the Supplemental Material.W The electronega-
last criterion excludes many types of compounds, for example: tivity values used were those of Allen et al. (19), expressed in
(a) Compounds with discrete dinuclear ions, which could Pauling units. For polyatomic molecules the weighted aver-
be described as both ionic (since they contain ions) age electronegativity defined by eq 7 was used rather than
and covalent (since some of the ions are polyatomic). the simple average.
(b) Molecular compounds, including clusters, which con- In this graph a triangular array of points is still obtained,
tain both homonuclear and heteronuclear covalent but there are some significant differences from the triangles
bonds. devised by other workers:
(c) Zintl compounds, which display some degree of me- 1. The compounds of a given element no longer lie on a
tallic interaction as well as containing simple cations single line (Cs and F) or a pair of converging lines (all
and extended polyatomic networks of covalently other elements). Instead a number of lines, converg-
bonded atoms, each with a formal negative charge (1c). ing at the position of the element, are obtained; for
example, all monofluorides lie on one line, all
(d) The group 1 compounds M3E of the group 15 ele-
difluorides on another line, and so forth.
ments As, Sb, and Bi, whose structures feature homo-
nuclear intermetallic bonding as well as heteronuclear 2. Some of these lines (polyfluorides, caesium compounds
interactions (26a). The group 2 compounds M3E2 of of multiply-charged anions, etc.) extend outside the
these elements also display some metallic properties. boundaries of the Cs–CsF–F2 triangle. This necessi-
tates a relocation of the vertices, to produce a triangle
(e) The suboxides of rubidium and caesium, which con-
that includes all compounds. The metallic and cova-
tain cationic clusters of identical atoms, such as M94+
lent vertices can be defined as the points with (∆χ =
and M116+, associated through metallic interactions
0, (χav)w= 0) and (∆χ = 0, (χav)w = 5); the ionic vertex
(1c).
would then be at (∆χ = 5, (χav)w = 2.5). This enlarged
The above criteria were applied to 321 binary com- triangle includes all well-defined compounds of the
pounds, formed by the elements of groups 1, 2, and 12–18 main-group elements. Figure 4 shows that there is good
in periods 1–6,4 in which the bonds are described by Green- discrimination among predominant bond types.
5.0
4.5
4.0
Electronegativity Difference / PU
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Figure 4. Bond triangle for well-defined substances: circles = mainly ionic, squares = mainly
covalent, and triangles = mainly metallic.
Covalent–Ionic Boundary
2.5
Electronegativity Difference / PU
Compounds specified as covalent and those specified as
ionic are well separated by a straight line with the equation
2.0
∆χ = 0.62(χav)w, as shown in Figure 4. This suggests that bi-
nary compounds with partial atomic charges greater than
±0.31 (per bond) are predominantly ionic, while those with 1.5
qA values less than 0.31 are predominantly covalent. This find-
ing contrasts with Pauling’s implication (13) that 50% ionic
character marks the dividing line. 1.0
There is a small triangular region adjacent to the “cova-
lent–ionic” and “covalent–metalloid” boundaries—the third
0.5
side being the dashed line in Figure 4—which contains very
few compounds specified as ionic or covalent. We will ob-
serve later that most of the compounds generally regarded as 0.0
being intermediate between ionic and covalent occupy this 0.5 1.0 1.5 2.0 2.5 3.0
region. A few compounds do not appear in their expected
regions of the triangle; most of these can be categorized as Weighted Average Electronegativity / PU
follows: Figure 5. Portion of bond triangle showing intermediate substances:
1. The 14 compounds InCl, InBr, InI, GaCl, GaBr, GaI, circles = covalent–metallic, squares = covalent–ionic, and triangles
= ionic–metallic.
TlCl, TlBr, TlI, PbCl2, PbBr2, PbI2, BiF3, and Bi2O3,
specified as ionic, are in or very near to the “covalent”
region. (Five are in the small triangular region de-
scribed above.) It is possible that the misplacement of
these “subvalent” compounds arises from the defini- pounds are known to be metallic. There is a substantial gap
tion of χ as the average one-electron energy (εl) of all in Figure 4 between compounds specified as metals and those
of the valence electrons of an atom (7); for an atom specified as nonmetals. The borders of these two regions in
with the configuration snpm: the triangle appear to be defined by curved lines, which could
well mark the boundaries of a metalloid or semiconductor
n ε s + m εp region. However, linear boundaries cannot be ruled out at
χ = (10) this stage
n + m The alloys LiBi and NaBi are very close to the interme-
diate, metalloid region in spite of having “typical alloy struc-
The predominately ionic character of these compounds
tures” (26a). They would be in the middle of the “metallic”
suggests that the metal atoms have electronegativities
region if the electronegativity of Bi were assessed only from
considerably lower than those obtained from eq 10.
the energy of its 6p orbitals, 0.599 Rydberg = 1.38 PU (19).
This would be consistent with the s electrons of the
metal taking little (if any) part in bonding, so that in-
cluding εs gives erroneously high χ values for these el- “Intermediate” Substances
ements, hence low ∆χ and high (χav)w values for their
The boundaries between bonding regions can be defined
compounds with nonmetals. This would be especially
more closely with the aid of another graph of ∆χ versus (χav)w
pertinent for compounds of Tl(I), Pb(II), and Bi(III),
values, plotted in Figure 5 for 62 substances (8 elements and
whose 6s orbitals are considerably stabilized by rela-
54 compounds) that are usually described as “intermediate”.
tivistic effects (27). (Apparently all subvalent ionic
These are also listed in the Supplemental Material.W They
compounds are misplaced, except SnO, PbO, PbF2,
are further categorized as follows:
and TlF). Only two other compounds specified as
ionic—MgI2 and MgSe—are in the “covalent” section. Covalent–Ionic (23 Compounds)
2. The only compounds specified as covalent that appear Eighteen of these compounds are within the small tri-
in the “ionic” region are the polymeric species HgO, angular area described above, separated from the “covalent”
PbF4, SnF4, SnF2, and GeF2. This is another instance region by the dashed line in Figures 4 and 5. Of the other
of the qualitative nature of the agreement between pre- five, AlN is on the “covalent–ionic” boundary, two (Cd3N2
dominant bond type and location in the bond triangle. and Zn3N2) are in the “ionic” region although quite close to
As noted above, the ratio ∆χ:(χav)w is not directly pro- the “covalent–ionic” boundary, and two (SnS and PbS) are
portional to partial charge,5 even in polyatomic mol- in the “covalent” region but very close to the triangular area
ecules. containing most of the intermediate compounds. ZnSe, BeSe,
CdSe, and Be2C are very close to the metalloid region; Shriver
Metal–Nonmetal Boundary and Atkins (28) describe Be2C (and Al4C3) as “borderline
between saline and metalloid”, and an ab initio calculation
It is very difficult to establish the border between met- (29) suggests that Be2C is largely ionic. CdSe is a semicon-
als and nonmetals, since very few stoichiometric binary com- ductor with a band gap of 1.7 eV (30).
Covalent–Metallic (34 Substances) cally by optimizing the sorting of a set of elements and
The eight metalloid elements and 17 of the 26 “cova- binary compounds that have been qualitatively char-
lent–metallic” compounds are in the metalloid region defined acterized as being predominantly ionic, predominantly
above. AlSb and InSb are just inside the “metallic” region, covalent, or predominantly metallic in their bonding.
and GaSb is on the border between metals and metalloids. Such a sorting procedure is at best only
The location of the semiconducting sulfides and selenides of semiquantitative, since we have no independent quan-
As, Sb, and Bi well inside of the “covalent” region seems very titative measure of predominant bond character.
anomalous. 4. Compounds of intermediate bond type also occupy
specific sections of the triangle.
Ionic–Metallic (5 Compounds)
(a) Most metalloids and semiconductors occupy an
These are also in the metalloid region. The somewhat area bounded by two curves, one separating them from
saltlike (26b) intermetallic compound CsAu, containing a metals and the other separating them from insulators.
transition metal with electronegativity 1.92 PU (31), would
be on the metal–nonmetal boundary. (b) Most compounds generally regarded as interme-
Thus the diagram for intermediate substances indicates diate between ionic and covalent occupy a small, nearly
that: triangular region adjacent to the covalent–ionic and
covalent–metallic boundaries.
1. The metalloid–nonmetal boundary is curved. A
straight line, drawn from the metalloid–nonmetal bor- 5. In spite of the limitations mentioned above, the posi-
der of the elements along the edge of the region occu- tion in the triangle of a binary compound of main
pied by compounds specified as covalent and ionic, group elements gives a reasonable indication of its pre-
places most known semiconductors among the pre- dominant bond type. Lecturers and textbook writers
dominantly covalent compounds; a straight line be- should bear the limitations in mind and point out that
tween covalent compounds and semiconductors places the great majority of compounds contain bonds that
several predominantly ionic compounds—the iodides, are in fact intermediate between two (or more) types,
hydrides, sulfides, and selenides of the group 1 met- even if they are predominantly of one kind. The exist-
als—among the semiconductors. ence of well-defined intermediate ionic–covalent and
The curvature of the metalloid–nonmetal line suggests metal–nonmetal regions of the triangle, both of which
that the metal–metalloid boundary is probably also a contain very few species having one predominant bond
curve rather than a straight line. All of the covalent– type, is also notable.
metallic and ionic–metallic substances examined lie 6. Applicability of the bond triangle appears to be lim-
between or very close to the region between two curves, ited to simple binary compounds. Even for those, the
as noted above. classification of Zintl compounds and others contain-
2. There is an “intermediate” covalent–ionic region in the ing polyatomic ions, and of suboxides and other clus-
bond triangle. Most compounds of this type occupy a ter compounds, presents some difficulties. Such
small triangular area adjacent to the covalent–ionic and compounds clearly contain at least two distinct types
metal–nonmetal boundaries. Of the “specified” com- of bonding, and the bond triangle in its present form
pounds, only a few subvalent ones and BeCl2, BeBr2, cannot represent this.
MgI2, and MgSe are in this area. The latter four com- 7. The usefulness of the bond triangle for categorizing
pounds could well be described as intermediate. compounds of the main-group elements may be ex-
tended by the use of weighted average electronegativi-
Summary ties to allow distinction between compounds of the
1. The dependence of bond type on the two parameters same elements with different stoichiometries. In such
∆χ and (χav)w is examined. It is shown that, for di- cases a higher valency for the central atom leads to
atomic molecules, greater covalent character and the compounds may
have different bond types.
(a) The extent of ionic character in a bond depends
on the partial charges on the atoms, which for diatomic
molecules is proportional to the ratio ∆χ:(χav). W
Supplemental Material
(b) Metallic character is governed by the gap between
the highest occupied molecular orbital and the lowest A list of the substances specified as being one predomi-
unoccupied molecular orbital, which is related to nate type or an intermediate type are available in this issue
c1(∆χ)2 + c2(χav)2. of JCE Online.