Edited by
MURIELBOY0 BISHOP
Identifying Polar and Nonpolar Molecules
R. J. Tykodi
Southeastern Massachusetts University, North Dartmouth, MA 02747
We touch on the polar/nonpolar character of molecules a t
various places in the undergraduate chemistry curriculum--
lightly in general chemistry and more in detail in physical
chemistry and in advanced inorganic chemistry:
nonpolar molecule.The center of positive charge in the molecule
coincides with the center of negative charge, and the molecule has
a zero electric dioole moment.
polar molecule. The centers of pmitive and negative charge fur
the molecule do not coincide, and the rndecule h a a nonzero
electric dipole moment.
With respect t o nonzero electric dipole moments, we ask if
a given molecule has one and, if so, what effect the dipole has
on the behavior of the molecule. The dioole moment of a
molecule is an ingredient in iw dielectricconntant (relative
permittivity) and in its molar uolarization. The behavior of
the dipole moment during a ;ormal-mode vibration of the
molecule determines the spectroscopic activity of that par-
ticular mode-if the vibrational motion changes the dipole
moment, that particular normal mode is IR-active (other-
wise not): the symmetric stretching vibration in COz, for
example, is IR-inactive (no change in the dipole moment)
and Raman-active.
We expect dipole-iipole interactions among the mole-
Murk1 Boyd B i s l w received the BA degree
In chemisby from Huntingdon College, the MS
degree in biochemistry from E m University,
and me PhDdegree in cheminryhom Michigan
State University. She received a porflactaal
appointment at Yale University. She Is current-
ly a profesor in the Chemistry Department at
Clemson University where she has taught
courses in biochemistry, organic chemisby.
general Ehemishy, and medical technology.
She has been director of the medical technoi-
ogy program, coordinata of the freshman
chemistry laboratories and of the freshman learning center. She devel-
oped me safety and teacher mining program for chemistry teaching
assistants. She has operated a summer science camp in chemistry for
high schwl students. She has worked with the Journal a number of
years, refereeing manuscripts. writing book reviews, and writing p s
pers.
Clemson University
Clemson. SC 29631
cules of a substance t o have an influence on its physical
properties; i t comes as a surprise, therefore, to find that the
influence of dipole moment on normal boiling point is quite
erratic: if we look a t the boiling points of sets of isomeric
molecules with identical molar-masses but varying dipole
moments, we find no clear trend with increasing dipole mo-
m e n t s e e the table (the reoorted dioole moments were
measured in the gas phase (1)j.
Determinine the centers of oositive and neeative charae
for a molecul~can be a forbidding task, so we frequeniy
resort to symmetry considerations (3, 4 ) to establish the
presence or absence of a nonzero electric dipole moment for
a -aiven molecule: a molecule is nonuolar (has a zero electric
dipole moment) if it has two or more noncoincident proper
rotation axes or if it has a center of symmetry ( 3 ) .Dealing in
detail with bond dipole vectors, with symmetry operations,
and with group-theoretical consequences of symmetry oper-
ations is appropriate in both the physical chemistry and the
advanced inorganic chemistry courses because these ideas
will be used in the discussion of molar polarization and
spectroscopic activity; such detailed considerations are not
appropriate to the general chemistry course because they
will not have any additional applications beyond the polar/
nonuolar cateaorization of a few simde molecules.
~ b much
w time and effort shouldwe devote to the polad
nonpolar character of molecules in general chemistry? Not
much-one or two lectures should be adequate. Once we
have identified the polar or nonpolar nature of a given mole-
cule, we don't do a&hing withthat information-we don't
usually say much about molar polarization or about the
details of s~ectroscooicactivitv in our aeueral chemistrv
courses, and we don't find an;special rilevance of dipoG
character to the nhvsical orooerties of the substances we
study (except for'soke q;ali&tive observations about the
nature of polar and nonpolar solvents). The polarlnonpolar
character of molecules is one of those "define i t and drop it"
todcs that so litter the landscaue of general chemistry. For
such isolated topics that are mostlyaithout ramifications
for the rest of the course, i t is important not t o "overspend"
in terms of time and theoretical machinery: do what you feel
needs doing, a t the simplest possible conceptual level, and
move on. I consider the PLAT0 module in Chemistry 1 (4)
on molecular symmetry to he an example of "overexpendi-
ture"in that it invests heavily in the machinery of symmetry
operations-an investment that does not "pay off' because
nowhere else in the course is i t needed or used.
Volume 66 Number 12 December 1989 1007
 EIectrb Dipole Moments and Bolllng Points lor Sets of Isomeric tion of the reference points is not fully symmetric, the mole-
Molecules ( 42) cule is polar.
For purposes of symmetry analysis, resolve a geometric
Molecule Diode momentldebves Boillna Point/'C fieure into a set of suhfieures that show either a center of
symmetry (the line) or multiple noncoincident proper rota-
tion axes (the trianele. the tetrahedron. the ~ e n t a e o n .the
square antiprism, &d so on). I shall call such kbfi&re$ the
"simple parts" of the given geometric figure.
If the satellite points of each of the "simple parts" are
equally occupied (occupied by identical entities), the refer-
ence figure is fully symmetric and the molecule is nonpolar.
CdWr If any of the "simple parts" has its satellite points unequally
1,ldichlamthane 2.06 57.3 occupied (occupied by nonidentical entities), the reference
1.2dichlw0ethane (less?) 83.5 figure is not fully symmetric, and the molecule is polar.
CIH+ Let's catalog some of the possible satellite configurations.
ethylarnine
dimethylamine onesolellilr: reference f i ~ r the
e line, h u w a t . If the two point aare
equally occupied, H-H for example, the molecule is nonpolar. If
CaHsCl the two pointa are unequally occupied. H-<I for example, the
frans-l-chlaopmpene molecule is polar.
3-chloropmpem, two satellites: reference figure the line, Sat.-huwat. (the line has
cis-l-chlaopropene hut one "simple part", the line itself). If the two satellite positions
2-chforopropene are equally o G i e d , C=C=O for example, the molecuie is non-
4HsCIa polar. If the two satellite positions are unequally occupied,
1.ldichlwopmpane O=G=S for example, the molecule is polar.
2,2dichlwopropane three satellites: reference figure the triangle (the triangle has hut
1,Michlwapropane one "simple part", the triangle itself). If the three satellite posi-
1,2dichlnaprapane tions are equally occupied, BF3 for example, the molecule is non-
CsHICI polar. If the three satellite positions are unequally occupied,
Z-chloropropane SnC4 for example (one of the points is occupied by an s/p lone
1-chloropropane pair of electrons), the molecule is polar.
CsHoN
I-amlnopmpane
blmethylamlne
C4He
1-butyne
19-bumdime
1,3-butadiene triangle BF3, nonpolar SnC12, polar
C~HH.
2-memylpmpene four satellites: reference figures the square and the tetrahedron (the
I-butene square has as its "simple parts" the two corner-to-corner diagonal
ci~2-butene lines, whereas the tetrahedron has hut one "simple part", the
trans-2-butene tetrahedron itself). If the "simple parts" of the square each have
CeH&Is their satellite positions equally occupied, tram-Pt(NH&Cln for
pdichlorobenrene example, the molecule is nonpolar. If either of the "simple parts"
mdichlwobenzene has its satellite positions unequally occupied, cis-Pt(NHa)pClzfor
pdlchlorobenrem, example, the molecule is polar.
CM+
pflUOmlOlUBnB
Sat.HSat. HaNMCI ClMNH3
mtluoromluBne
ofluomtoluene
Sat. Sat. CI
- ~ NHq" C1 NHq
square (trans) nonpolar (cis) polar

If the satellite positions of the tetrahedron are equally occupied,

What I want to do in this paper is to develop a scheme, CHI for example, the molecule is nonpolar. If the satellite positions
based on the most elementarv ideas of molecular svmmetrv. .. of the tetrahedron are unequally occupied, CH3C1for example, the
for determining the polar/nonpolar character of simple mol- molecule is polar.
ecules-a scheme suitable for general chemistry and that
can be used as astartingpoint for the more general consider-
ations of svmmetw develo~edin uhvsical chemistry and in
advanced inorgan& chemistry.
Simple Molecular Clusters --

Let's start by considering simple molecular configurations
where a central hub atom is surrounded by a set of satellite
entities (atoms, molecules, or s l p electron pairs (5): Con,
H20, BF3, CHC13, Ni(CO)a, PC15, IF&,SFs, etc.
Associate with each simple molecular configuration a geo-
metric fieure such that the huh atom is a t the center of the
figure &d the satellite entities occupy the vertices (or
points) of the figure. If the satellite entities-the satellites,
for short--occupy the points (vertices) of the figure in afully
symmetric fashion, the molecule is nonpolar. If the occupa-
tetrahedron CH,, nonpolar CH3C1, polar
I think you get the general idea by now, so I'll look a t just
two more commonly occurring geometries, the trigonal bi-
pyramid and the octahedron.
Trigom1 bipyramid: the "simple parts" are a vertical line and an
equatorial triangle. If the satellite positions of the line and of the
triangle are equally occupied, the molecule is nonpolar. If the
satellite positions of either the line or the triangle are unequally
occupied, the molecule is polar. Here are a few examples:

1008 Journal of Chemical Education

 \ I

/c=C\
H CI
Sat. trans-1,2,dichloroethylene,
trigonal PFs, nonpolar PFJCIZ,polar nonpolar
hipyramid
The presence of the double hond in ethvlene confers rieiditv
P C1 F on &e molecnle and makes for fmed bond angles close tb
120°. We can find acentral point in the molecular configura-
tion (halfway between the two carhon atoms) such that the
pencil of lines radiating out from the point contains three
k 61 i lines that skewer the atoms of ethylene, two a t a time, in a
PFzC13, nonpolar TeCla, polar XeF2, nonpolar balanced way (the vertex of the pencil is a center of symme-
Octahedron: The "simple parta" of the octahedron are the three trv for ethvline).
comer-to-corner lines that pass through the center of the figure. If "Take t h l indicated three lines of the pencil as the "simple
the satellite positions of each of the three lines are equally occu- narts" of the eiven eeometric confieuration: then. since the
pied, the molecule is nonpolar. If the satellite positions of any of ieference points of e a c h of the lines are e&ally'occupied,
the three lines are unequally occupied, the molecule is polar. Here ethylene must he nonpolar.
are some examples: Use the same vertex and pencil of lines for each of the
Sat. F three dichloroethvlenes. and take the three skewerine lines
as "simple parts'. hen 1,l-dichloroethylene and cis-1,2-
dichloroethylene contain lines with reference points that are
unequally occupied, so they are both polar molecules. The
reference points on each of the lines in trans-1,2-dichlor-
skt. oethylene,-however, are equally occupied, so the molecule is
nonpolar.
octahedron SFs, nonpolar If we look a t the electronegativities (Pauling scale) of
F .. carhon, hydrogen, a n d chlorine-C(2.60), H(2.20),
Cl(3.15)-we see that we could have anticipated the ~ o l a r
nalure of 1,l-dichloroethylene and of cis-1;2-dichlorokthy-
lene iust hv lookine at the structural formulas: the chlorine
.. .. side kf t h e molecuie should be negative and the hydrogen
side should he positive. causina a separation of charae ' that
IF5, polar XeF4 nonpolar should result in a nonzero elecGic dkole moment.
In treating simple molecular clusters of the kind we have Next let's study hydrogen peroxide and hydrazine.
just been looking at, we need hut acquaint our students with
the "simple parts" of the few reference geometric figures
that show up over and over again. General chemistry stu-
dents then seem t o have little trouble in applying this
scheme to the determination of the polarlnonpolar character
of common molecules. hydrogen peroxide, polar hydrazine, polar

Rlgld and Nonrlgld Chain or Tree Conflguratlons
Treating molecular clusters with single huh atoms is easy
enough, hut what do we do for molecular configurations with
several huh atoms: CzHs, CzHa, CzHzC12, H202, N2H4, C3H8,
etc.? We do what we can, in an eclectic fashion-sometimes
looking for charge separation, sometimes irradiating the
molecule with a pencil of lines (6) in a suggestive fashion, etc.
Rigid Configurations
Let us look first a t a few molecules with rigid or "locked-
in" configurations-an archetypical case would be that of
ethylene and some of its derivatives.
pencil of lines
1,l-di~hloroeth~lene,cis-l,Z,dichloroethylene,
polar polar
The configuration of bonding and lone pair electrons about
the huh atoms in each case is approximately tetrahedral:
H U O hond angles of 95O, H-N-H hond angles of 108°.
Consider hydrogen peroxide. If the four atoms were copla-
nar. with the hvdroeen atoms in a trans confieuration. then
we could irradcate &e molecule with a pencil of lines from a
central point and skewer the atoms in a balanced fashion-
the pl&ar configuration would he nonpolar. The actual con-
firmration of H?O?. however. is such that the two H-0
bonds lie in different planes, the dihedral angle hetween the
planes heine about 111.5°. and the molecule is polar.
- Here is agood place t o introduce a useful r& of thumb:
If it ispossibleto arrange the atoms in agiuen molecular eonfigura-
tion insueh a way that, consistent with the experimental atom-to-
atom bond angles, there is a central point from which a pencil of
lines skewers the atoms of the configuration in a balanced fashion
and if the actual experimental configuration differs from this ref-
erence (nonpolar)configuration by a reorientation of the parts of
.. . rotations.. ete.)... then
the maleeule relotiue to each other lfoldines.
the expenmental cnnftpurotion hos a nomero eleelnr dipole mu-
ment (i.e., the molecule rs a polor rnnlerulej.
According to our rule of thumb, then, hydrogen peroxide
should he, and is, a polar molecule.
The same sort of argument applies to hydrazine. If we hold
one NH2 group fixed and rotate the other NH2 group until
the two lone-pair charge clouds are exactly "diagonally op-
posite," there will be a central point that can serve as a
vertex for the right sort of pencil of lines. The actual experi-

Volume 66 Number 12 December 1989 1009

mental configuration differs from the reference configura-
tion by a rotation ahout the N-N axis: hydrazine exists in a
gauche form with a twist angle of -9@, the twist angle
measuring the departure from a fully eclipsed configuration
(the twist angle of the reference, nonpolar, configuration
would he 180"). According to our rule of thumb, hydrazine
should be, and is, a polar molecule.
Let us also look a t some benzenes.
benzene nonpolar pencil of lines
1,2-dichlorobenzene, 1,3-dichlorobenzene.
polar polar
C1
Cl
1A-dichlorobensene,
nonpolar
The center of the hexagonal configuration of benzene can
serve as thevertexfor a pencil of lines, three of which skewer
the atoms of benzene in a halanced fashion. Let the three
indicated lines of the pencil serve as the "simple parts" of
the configuration-do the same for the dichlorobenzenes.
Each of the lines in benzene and in 1.4-dichlorohenzene has
reference points that are equally occupied,so both molecules
are nonoolar. Both 1.2- and 1.3-dichlorohenzene have lines
the refeience points of which are unequally occupied, so they
are both polar molecules.
Again, the electronegativity difference between chlorine
and carbon would have led us to expect that 12- and 1,3-
dichlorobenzene should each have a nonzero electric dipole
moment.
Nonrigid Configurations
When narts of a molecule can freelv rotate. fold, or flap
relative & other parts, we deal with thetime-average propei-
nonpolar configuration-so we expect ethane to behave as a
nonpolar molecule.
I t is clear from the electroneeativitv . areument
.. that 1.1-
dichloroethane should be a polar molecule. The line of the
effective charee doublet of the dichloromethyl group will be
skew to the C% line, and there will be a n i t separation of
charee in the molecule-the molecule, therefore, will possess
a no&ero electric dipole moment.
The case of 1,2-dichloroethane requires some care. The
lines of the effective charge doublets of the chloromethyl
groups will each be skew to the C-C line, but the two skew
lines could be so oriented that a suitable pencil of lines could
skewer the effective charges in a balanced fashion. For pur-
poses of analysis, fix one chloromethyl group in place and
then rotate the other group until the two chlorine atoms are
exactlv diaeonallv o ~ ~ o s i each t e other (the configuration
ahoutveach"carb~nitom is tetrahedral). In the reference
confieuration there is a central point from which a pencil of
l i n e s i l l skewer all the atoms of the molecule in a balanced
fashion, so the reference configuration is nonpolar. Now if
we rotate our nonfixed chloromethyl group away from the
"exactly diaponally opposite" configuration to any other
configuration, we have, by our mle ofthumb, a polar config-
uration. In one complete rotation of the nonfixed group,
therefore, we pass through one nonpolar configuration and
an infinite number of polar configurations; so, on a time-
averaee basis.. Id-dichloroethane
. must behave as a polar
molecule.
Finallv. let us look a t the series of straight-chain (alkane)
hydroca;bons: propane, n-butane, n-pent&e, n-hexane, etc.
Consider separately the odd series (odd number of carbon
atoms) and the even series (even number of carbon atoms).
For a member of the odd series, select the carbon atom a t the
center of the chain and look a t its tetrahedral environment,
considering the H atoms as charge singlets and the organic
radicals as effective charee doublets (Me-methvl. Et-ethvl,
etc.). The odd straight-:hain (alkane) hydroc&bons have
reference tetrahedral configurations with points unequally
occupied, so they should all be polar molecules.
For a member of the even series, select the two central
atoms and treat an organic radical attached to a central
carbon atom as an effective charge doublet. The appended
organic radical plays the same sort of role here as is played
by a chlorine atom in 12-dichloroethane: in the course of its
internal rotations about its C-C honds, the molecule passes
through some polar configurations; so, on a time-average
basis, the molecules of the even series (C4Hm. CsH14, etc.)
should behave as polar molecules.
All the molecules in the series of straight-chain (alkane)
hydrocarbons, starting with propane (CsHs, C4H10, C5H12,

ethanes.
- - wav- of example,
ties of the confieuration. Bv . . consider some etc.), should, therefore, behave as polar molecules. The elec-
tronegativities of carbon and hydrogen are sufficiently close
together [C(2.60), H(2.20)], however, so that the individual
honds of such a hydrocarhon are hut slightly polarized; and
H H C1 H H H the total effect of the (weak) bond polarities is but a small
-H - - E l nonzero electric dipole moment. For each of the molecules of
the series propane to n-octane the dipole moment is less
H H
I I
H H H
I HI than or equal to 0.1 debyes (I).
There are, of course, some branched (alkane) hydrocar-
ethane, 1,l-dichloroethane, 1,2-dichloroethane. bons that are nonpolar, neopentane, for example.
nonpolar polar polar

In ethane the two methyl groups are free to rotate about

the C-C bond, so we have to consider the time-average
configuration of the molecule. For purposes of finding the
centers of positive charge and of negative charge in the
molecule, we can treat a methyl group as an effective charge ~e H fl Me
doublet. with the negative charge on the carbon atom and propane, n-hexane, polar neopentane,
the effective positive charge contribution of the three hydro- polar 2.2-dimethylpropane,
gen atoms located on the C-C line. We thus have, in effect,
equal occupation of a set of reference points on a line and a polar

1010 Journal of Chemical Education

Conclusion
I recommend that we spend some time teaching our gener-
al chemistry students how to recognize polar and nonpolar
molecules via the application of eliment&y symmetry ideas
in the manner demonstrated here-"simple parts" of refer-
ence eeometric fieures. the irradiatineoencil of lines and the
rule of thumb, Gc. I k g e that we k t our treatment of
symmetry in general chemistry to the bare essentials, saving
the sophisticated treatment of symmetry and its ramifica-
tions for the upper division courses in physical chemistry
and advanded inorganic chemistry.
Literature Cited
Nelson, R. D., Jr.: Lide, D. R.. Jr.: Maryott, A. A. S&&d Values of Electtie Dipole
Mompnfs for Moleeulea in tho Gas Phase: Nationd Bureau of Standards Referonce
Data Seri-National Bureau of Standards 10 (NSRDS-NBS 10). 1967.
Hondbwk of Chemistry end Phyaica, 67thed.; CRC: BocaRaton, FL, 1986.
Lwine. I. Quantum Chemistry. 2nd ed.;Allyn and Bacon: Boston. 1974:Chapter 12.
PLATO, Chemiafry 1: Contml Data Corp., 1983; module H.
Lone and lone mir electrons derivine: from s and/or P e1eNor.s have an influence on
Volume 66 Number 12 December 1989 1011