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DAN KALLUS
Midland Senior High Schwl
906 W. Illinois
Midland. TX 79705
chemical principle/
ted
revi~i
RUSSELL D. LARSEN
Texas Tech University
Lubbock. TX 79409
'
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Nat(g) + e-
CKg) + e-
(1)
. - -.
-- ..
character
Covalent Bonds
We were able to discuss ionic bonding without any recourse to quantum mechanics, although a quantum mechanical calculation on NaCl(g)eprovides an essentially ionic picture of the bonding. For covalent bonding, we can again
avoid any explicit use of quantum mechanics for afirst-level
introduction. After all, Lewis proposed his electron pair idea
and the octet of electrons in 1916, several years before the
onset of modern quantum mechanics in 1925. Therefore we
begin this discussion of the covalent bond with a thorough
treatment of the Lewis electron-pair idea and proceed from
there to a more formal understanding of the covalent bond.
Lewis Electron Dot Structures (LEDSj of Simple Molecules
In Figure 2 we present the usual LEDS for several simple
molecules. These examples suffice to point out the concepts
of (1) electron pairs, (2) octet of electrons, (3) lone pairs vs.
hond pairs, and (4) single bonds vs. multiple bonds. LEDS
are also foundational for (1) nredictine which molecular
systems will be extremely reactive, (2) predicting molecular
shape via the valence-ahell electron-pair repulsion method,
&
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Applications of LEDS
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-----I
tetrahedral
+--e
I'
uipnal pyramidal
Type of
Hybrid Orbitals
Rewlting
Structure
two
three
four
SP
sp2
sp3
linear
trigonat pianav
tetrahedrain
far a pocket computer to tell what you are supposed to say when
seeing a given chromophore.
most stahle connectivities of the atoms in a molecule can he
deduced by a simple nuclear repulsion theory. We here employ LEDS to accomplish a similar goal. Suppose we are
asked to nredict the molecular structure for the molecule
HC'OF, which has I 8 valence electrons. Will this molecule be
linear HCOF. HOCF. HFCO. HFOC. HOFC, or HCFO'! Or
will i t be nonlinear, and if so,'will i t be plana;?
We have developed a set of emdrical "rules" that seem to
he valid for the irediction of tl;e most stahle topology of
many molecules (11). These rules are not foolproof, hut they
do p&ide reasonahk guidelines for deducing stahle topoloriesof molecules. The priority oftherulesshuuld be taken in
the order listed
1. Hydrogen atoms are terminal. Example: HCN not CHN.
2. For two elements from the same row in the neriodic chart. the
rlemrnt fanhrr to thr right will be terminal. Example: HCN.
The H N C isomer is lefisscablr.
~
~~~
The first structure is the proper one for the most stahle isomer
of HCN.
Applying these rules t o the molecule HCOF, we can write
three isomers, each involving a different topology:
The first structure best obeys rules 2 and 5, and this structure corresponds t o the most stable isomer of HCOF.
Hybridization. The concept of hybridization of orbitals
was first introduced by Pauling (12). The author agrees with
Jorgensen (13):
The hybridization model was a refreshinginnovation,when it was
introduced by Pauling in 1931, hut the commentators in texthooks have gone very far along a sterile scholastic desert trail. The
main field of use today is describing hond angles, but the conclusions are a posteriori. It would he easy to construct a programme
../s,..
-, . 0;
0:
s\..
Number 11
November 1987
937
"Aobnced" LEOS
We have touted the advantages and disadvantages of simple LEDS. The Generalized Valence-Bond (GVB) method
(19)represents one way in which LEDS can be enhanced in
order to overcome some of its deficiencies. In the GVB method one keeps track of the type of atomic orhitals that are
used t o form chemical bonds. For example, the usual electronic configuration of the fluorine atom is presented as 1s2
2s2 zP: 2p$ ZP& In the GVB method this is depicted as
938
Distance
Figure 6. The total energy W, the average eiectmn kinetic energy T. and the
average diatomic potential energy V of HZ. ploned as a function of the
internuclear distance. The units are the same as in Figure 5. This figure has
been taken from Winn. J. S. J. Chem. Phys. 1981. 74,608.
+H
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GAS
METAL
Figure 9. Schematic plot of lhe total energy of a collection of Be atoms for the
s2 and sp electron configurations as a function of internuelear distance.
a.
1. P s ~ rR.
, G.McCrolu HilIEneyrlopedioof Chemisfry,Parker,S. P.,Ed.: McCraw-Hill:
0 contains the strong bonds. The points labelled E and F refer to N2 and CO.
respectively.
..".,
19Ld f-.
ir , l l d
7. Ref 4, pp 93-101.
8. Gillespie, R. J. J. Chem.Educ. 1963.10.295: 1910.47.15: 1974.51,367.
9. Schmiedekamp,A.:Cruickschsnk,D. W.J.:Skaarup,S.;Pulay,P.;Hargittai,I.;Bngga,
J.E. J.Am Chem.Sac. 1979, lol,2002. Bade?,R.F. W.:MacDougall,P.J.;Lau,C.
D.H. J.Am.Chem.Soc. 1984,106,1594.I.indner,P.:Lunell,S.Chem.Scripta 1984,
24,105.
10. Pauling, L.; Hendricka. B. J. Am. C h m So<. 1926,4S. 641. Pauling, L. J. Chem.
Edur. 1975.52.577.
11. R e L 4 . p ~115-119.
12. Pau1ing.L. J. Am. Chrm.Soc. 1931.53, 1367.
13. Jorgensen,C. K. Topics Current Chem 1984,124. I.
14. Magnu8son.E. J. Am. Chrm.Soe. 1984,106,1177.
15. Pading. L. Pror Noll. Acod. Sci. USA 1984.81, 1918, Pauling, L.: Hsrman, 2. S. J.
Chsm. Educ. 1984.61.582.
16. Pauline, L., The Notura of the Chemical Bond, 3rd d;Cornell Univ.: Ithaee. NY.
1960.
17. Mitchell. P. R.:Parish.R.V. J. Chem.Educ. 1969,46,811.
18. Carroll, J. A. J. Chem. Educ. 1986.63, 28.
19. G~ddard
W. A.,III: Ounning,T. H.,Jr.; Hunt, W. J.: Hay,P. J. Accts. Chsm.Rss. 1973,
S.
""-
",""o.
20.
21.
22.
73.
24.
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Number 11
November 1987
941