chemicd principle/
revi~i
ted
A Different Approach to Hybridization and Geometric
Structure of Simple Molecules and Ions
Diana Eberlln and Manus Monroe
lndian Valley Colleges, lgnacio Boulevard, Novato, CA 94947
When studvine - " the c o n c e ~ tof orbital hvbridization in
freshman and advanced secondary chemistry courses, many
students become readily confused about orbital hybridization
and geometric structures of simple molecules and ions. Simple
molecules and ions (charged radicals) are those which contain
from three to seven atoms, one of which is the central atom for
the structure. In most textbooks, after several pages of dis-
cussion about structrlres and orbital hybridization, an ex-
tensive summary table is presented to help reduce student
confusion. These summary tables often list the coordination
numbers, the number of bonded pairs, and the number of lone
pair electrons for molecules and ions without a specific and
direct statement about hybridization and structure. Many
students do not find these tables beneficial.
We present here a successul step-by-step teaching tecb-
nioue.
,~~,with detailed comments for student learning.
~~~~
.,. which
directly currelates hybridization with structure.
b i r s t . we remind studt:nts that ill reference tu simole mul-
ecules and ions that:
(1) When evaluating a formula, the central atam is the single atom
shown in the formula while the remainine atoms are lieands.
and SFBN.
(2) The geometry is controlled by the number of single bonds and
sets of lone pair electrons around the central atom.
(3) Single bonds are formed from hybrid orbitals while doubleand
triple bonds are formed from the overlap of p andlor d orbitals.
Pauling, Linus, "General Chemistry," 3rd Edition, W. H. Freeman
and Company, 1970, pp. 192-194.
Pauling. Linus, and Pauling. Peter. "Chemistry," W. H. Freeman
and Company, 1975, pp. 180-181.
Durant. Philip and Durant, Beryl. "Introduction to Advanced Inorganic
Chemistly." 2nd Edition, John Wiiey and Sons, 1970, pp. 530-531.
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valence electrons added to lhe sulfur atom toaccoum for the double negative
charge
Edited by
Charles D. Mickey
Texas A b M at Galveston
Galveston, TX 77553
Multiple bonds affect bond lengths, not the type of geometric
structure.
(4) Only nonmetal atoms of the second row (8, C, N, 0, F) con-
sistently follow the octet rule. These atoms have only s andp
orbitals available for hybridization and can readily obtain an
inert eas confieuration. All other central atoms. metal and
nmmeral, ma" haw more r h n n eighr valrnr~clectnms a i they
haw ,, p, and d orbitals nvailatde im hyhridimtion. Molerdm
and ions u h ~ hove
h a central atom that violates thr wrrr rub
are called complex or coordinated
Second, we review the concept of using formal charge to
draw structures. We remind students that the formal charge
of any atom in a molecule or ion is the difference between the
number of valence electrons that atom has in its bonded state
as compared with its nonbonded state, i.e., as if it were an
isolated atom. Since we are followine the basic conceot of
Linus Pauling's electroneutrality we call these
structures "Pauling Structures." We remind students:
(1) To first surround the central atom with its ligand atoms (e.g.,
sulfate ion, Figure 1A).
(2) To place around each atom the number of valence electrons
associated with its group number (Figure 1B). For noble gas
atoms, assume eight valence electrons. For negatively charged
ions, add one additional valence electron to the central atom
for each negative charge (Figure 1C). For positively charged
Fogwe 2 A. Ammonl~mon wlth one valenceelectron removed bom the no-
bogen atom la account tor a s ngle pos.tlve cnarqa B Ammma wlth the one
pair electrons affecting the location of bonding electrons.
Diana Eberlin is a stdem and Manus Monroe is an insbuctarat lndian
Valley Colleges PI- send all wrilten inquiries to Dr. Manus m r o e .
Novato, California 94947.
This feature is aimed as a review of basic chemical .orinciDles
. and as
a reappram1 ol me state ol tne m Comments, s~ggesllonslor lopes
m a conlroobt ons shobld oe sent to me lealure ed lor
Volume 59 Number 4 April 1982 285
Figure 3. Hydroxide ion. Figure 4. Ammonium ion. Figure 5. Paullng shrcture far boron trifluoride (resonance not shown).

ions, remove one valence electron from the central atom for
each positive charge (Figure 2A). We now inform students that
these rules are not applicable to the metal atoms of Group
VIII.
(3) To draw single bonds between the central atom and its ligands.
Now, we tell students to count the number of electrons asso-
ciated with each atom rememherine that in this teehniaue of

an atomis the same as itsgroup number, they must assign that

atom a formal charge of zero (e.g., ammonia molecule, Figure
28). If the total number of valence electrons associated with
1 Lewis Sbucture Pauling Sbucture
(Resonance not Shown)
an atom is greater than its group number, then assign that atom
a negative formal charge (e.g., hydroxide ion, Figure 3). If the
total number of valence electrons associated with an atom is Figure 6. Lewls (left)and Pauling (right)structures f a sulfate ion (resonance
less than its group number, then assign that atom a formal not shown).
positive charge (e.g., ammonium ion, Figure 4).
(4) That, for molecules,all the formal charges must add up to zero. (2) If the central atom needs four hybrid orhitals, we use four
Generally, the formal charge on each atom in a molecule is zero. atomic orbitals to make the required orbitals (concept of con-
For ions, all the formal charges must add up to the actual charge servation of orbitals). First we uses a n d p orbitals and, if nec-
on that ion. As a rule, atoms with higher electranegativity .. d orbitals for hvbridization. For examole.. since am-
essarv. .
values most often have negative formal charges (Figure 3) while monia has three sin& bonds end n set of lone "air electrons.
atoms with lower electroneeativitv values most often have
~ ~

positive formal charge+ F i ~ ~ l4).

r e The nunmetal at<rmslisted
m the second row un n per~odwchart generally do m,t fullow orbitals are required for single bond andlor lone pair electrons,
y rmdlly ohtam nn
these rules of formal charge hrrause t h ~ can we use m e v 1~rh1131, three p orbitals, aud one d d h l to rrelte
inert gas configuratiun and thereby tulluw the octet rule, fiverp'd or dsp 'orbitals. At thisspecific point. nr explain to
sometimes just by hnving multiple bonds. There 1s evldenre studentsthat these two hsbrididauon term,differ m l s m their
that cten boron trifluoridr follow the wtet r u l ~ ' h shming n desienation
" of which d oibital is beine" used in hvhrihizatian.
double bond (Fieure 5) For examole.
~ ~~
, ~if the ~ . ~
. ~~~ ~

quantum number, then the hyldiration term ap'd is written.

~
. s. o and d orhitals have the same ~rincinal
~~ ~ ~~~
.~~~
~ . ~~

(5) That, by drawing a multiple bond, the formnl charge m the

central atwn is redurcdand the formal rhargeon th~ligandis
increased in accordance with the rules of formal rhargr (e.g.,
sulfate ion, Figure 6).
Third, now that s t u d e n t s have drawn proper Pauling
S t r u c t u r e s (e.g., Figures ZB,3, 4, 5 and 6), we have t h e m
evaluate t h e structures for hybridization a n d geometry. We
review with s t u d e n t s t h e following concepts:
(1) Each single bond from the central atom requires a hybrid or-
bital. In addition, each set of lone pair electrons also needs a
hybrid orbital because of their influence on structure and
ability to form bonds.
Ifthed d h a l hnsaquantum nunlbcr lower than ther a n d p
orbitals, the term dsp3 is used. Since only extensive research,
including magnetic measurements, will determine which hy-
bridization term is correct, we inform students that writing
either term is acceptable. We further explain that, of these two
hvbridization terms. the" will most often encounter so3d hv- , .
hridizatim in freshman chemistry. If six hybrid urlitals are
required, then six p ' d ' o r d?spQhybrid whitalu are needed.
Of the*" two hyhndizations, the studen~swill most uftrn en-
n u n t e r apLd2 hybridisation. We also remind student; that
u,hen phosphorus, sulfur, and chlorine are central atcms, they
van only formrp'd or cp.'d2 hybrid orhitals herawe these n r
the first atoms to hare d orbitalsavailalrle for h?hridialtion.

Geornetrlc Structures and Hvbrldlzatlon

Number of
Hybrid Orbitals Outlined
Required Structures Sketch of Oeometric Structure Orbitals Ions of Molecules
TWO Linear - SP Linear
mree Triganal @ Trigonal Planar
Planar or Bent

Four 59 Teuahedral. Distorted

Pyramidal or Bent

Five Trigonal Trigonal Bipyramidai.

Blpyramidal DistoRed Tetrahedral,
T-Shape or Linear

Six Square Base ff spS Octahedral. Distorted

Bipyramidal Square Base Piramidal
(Octahedral) or Square Base Planar

286 Journal of Chemical Education

 Fourth, we explain to students that we orientate hybrid
orbitals from the central atom in accordance with the basic
concepts of solid geometry. In essence, two hyhrid orhitals are
placed in such a manner as to outline a straight line, three
hvbrid orhitals are nlaced in such a manner as to outline a
tGiangle, four hybrid orhitals are placed to outline a tetrahe-
dron. five hvhrid orhitals are nlaced to outline a trieonal bi-
anh six hyhrid orbit& are placed to outlinea square
base bipyramid or an octahedron (see table).
After students have correctly drawn Pauling Structures and
counted the number of single bonds and sets of lone pair
electrons, they draw the appropriate geometric structure as
shown in the table. If there are lone pair electrons, we instruct
the students to cover them with a nencil or their fineer when
wnluating structures. Now, we can readily discuss with stu-
dents that a trianeular arranrement of h\.brid orhitals either
forms a trigonal d a n a r s t r u c h e when the three orhitals are
used for bondinrr or forms a bent structure when one hvbrid
urhital is used for a set ot lone pair elrctrons.
Since manv of the molerulrs and iuns that students srudv
have a structure based upon a tetrahedron, we spend extra
time exnlorine this structure. We explain to students that a
tetrahedral arrangement of hybrid oibitals forms a tetrahe-
dron structure only when the four orhitals are used for
honding. The angle between each hond on the central atom
is approximately 10SD.When one hybrid orbital is used for a
set of lone pair electrons, a pyramidal structure with bond
angles of approximately 101° is formed. A set of lone pair
electrons reduces hond angles by approximately 2'. We ac-
curately call this structure a distorted pyramid. When two
hybrid orhitals are used for lone pair electrons, a bent struc-
ture with a bond angle of approximately 105O is formed.
We explore with students that a trigonal hipyramidal ar-
rangement of hyhrid orbitals forms a trigonal bipyramidal
structure only when the five orbitals are used for bonding.
Lone pair electrons are placed in hybrid orhitals that are on
the equatorial plane of this structure to reduce their disruptive
effects on honding orbitals. When a single set of lone pair
electrons are placed on the equatorial plane, a distorted tet-
rahedron is formed. When two sets of lone pair electrons are
placed on the equatorial plane, a T-shaped structure is
formed. When three sets of lone pair electrons are placed on
the equatorial plane, a linear structure is formed.
Finally, we explore with students the idea that an octahe-
dral arrangement of hyhrid orhitals forms an octahedron only
when the six orhitals are used for bonding. We remind stu-
dents that for an octahedron, the equatorial and axial posi-
tions are equivalent and that we traditionally place lone pair
electrons on the axial position for ease of seeing geometric
structures. When one hybrid orbital is used for a set of lone
pair electrons, a distorted square base pyramidal structure is
formed. When two hyhrid orbitals are used for lone pair
electrons, a square planar structure is formed.
In conclusion, this method of using Pauling Structures and
counting the number of single bonds and sets of lone pair
electrons allows students to quickly and accurately describe
the orbital hybridization and the structure of simple molecules
and ions.
Volume 59 Number 4 ADriI 1982 287