DIPOLE MOMENTS AND MOLECULAR

STRUCTURE

H. R. DAVIDSON
General Aniline and Film Corporation, Easton,
Pennsylvania

MEASUREMENT
of dipole moment is a fairly simple There exists, of course, an individual moment between
process, the apparatus required is relatively simple, and each pair of unlike charges, but if all of these individual
operation of the apparatus is well within the capabilities moments are added vectorially, the resultant will be
of any intelligent high-school student. Although the given by equation (1). It should be noted that the
exact interpretation of the meaning of dipole moment body shown in Figure 1is not charged: it has an equal
values is often obscured, relative interpretations, such number of plus and minus charges. The moment
as comparisons between two very similar molecules, are arises not from net charge but from a separation of
often quite simple and useful. In spite of these facts, charge. Thus if points A and B coincide, i. e., if there
however, there seems to be a considerable reluctance on is no net separation of charge, the moment is zero.
the part of organic chemists to make use of dipole mo- distorted electron orbit
ment measurements in determining molecular stmcture.
I t is the purpose of this paper to provide a simple re-
view of dipole moment theory, to describe apparatus
for use in dipole moment measurements, to describe a
simple procedure for makmg measurements and calcu-
lations and, k a l l y , to illustrate the usefulness of the
measurements by a few of the results obtained in this
laboratory. Except for these illustrative results, noth-
ing in this paper will be new. It is hoped, however,
that an elementary review of the theory and practice
will help to promote a more widespread use of dipole
-f
moment measurements. effective oharge separation
Fig- 2. Atomic Dintortion in en Electric Field
THEORY OF DIPOLE MOMENTS ( 3 . 4 , 6 , 8 )

A (center OI + charge) Each bf these will be considered briefly in the following

paragraphs.
When an electric field is applied to an atom, the or-
bits of its electrons are displaced from their normal posi-
tions so that the nucleus and electron orbits no loneer
Y Direstion or lie in the same plane. The centers of charge are thus
Electric Field
displaced from coincidence and a moment exists. This
effect is illustrated by the hydrogen atom in Figure 2.
The center of charge has been displaced by a small
amount, hence a moment equal to the charge times this
distance now exists. Each atom in a molecule may be
B (center of- charge) distorted in this manner. The moment so formed, how-
ever, is not permanent. It disappears as soon as the
~i.- l. uwtric D~PO~.
field is removed. This effectis sometimes known as op-
the center of plus charge is a t A, the center of minus tical polarization and is designated as Po in equations
charge is a t B, and the body is polarized. When this (4) d , (5) (page 602). Since the moment due to dis-
body is laced in an electric field, it will tend to rotate tortion is not permanent, it is excluded in calculation of
clockwise as shown in the figure until a line joining the dipole moment(see (5)).
points A and B is parallel to the field. If we call d the ~ h momeut
, setup in a molecule by unequal sharing
distance between A and B, and e the total negative (or of electrons can be illustrated schematically with the
positive) charge, then the moment (m) is simply: hydrochloric acid molecule shown in Figure 3. Here
rn = de (1) the electron pair which forms the bond between the hy-
598
NOVEMBER. 1950
drogen and chlorine shared electrons
atomsis held moretightly
by the chlorine atom.
This displaces the center
of negative charge toward
the chlorine atom while
the center of positive
charge remains un- Dipole Direction Of
Moment
changed. A dipole mo-
ment thus in figura 3. Dipole Formad i n HC1 by
Unequal Sharing of Elactro-
the molecule due to
the separation of the
centers of charge. By convention this moment is
considered directed toward the chlorine atom as shown
in the figure, or in the direction of the displaced elec-
trons.
The phenomenon exhibited by the hydrochloric acid
molecule in Figure 3 will exist to a greater or lesser de-
gree in the bond between any two unlike atoms. The
direction and an estimate of the bond moment may in
general be obtained from examination of the electro-
negativities given in Table 1. The moment will be di-
rected toward the more electronegative atom and will be
greater as the difference in electronegativity of the two
bonded atoms increases.
Electronegativities of Some Elements (7)
Element Eleet~oneoatitiitu Element Electroneoativitv
In the case of symmetrical molecules, however, the
resultant moment due to bondmg is zero. Consider the
molecules shown in Figure 4. Although a moment ex-
ists in each C-H bond, each of these moments is hal-
anced by the combined moments resulting from the
other C--H bonds. Since no permanent dipole moment
exists in these symmetrical molecules, they are called
nonpolar. When placed in an electric field they will, of
course, have a moment, but that moment will be due to
distortion, not to unequal sharing of electrons.
In Figure 5 are shown several polar molecules, that is,
molecules with a permanent dipole moment. I n the
case of these asymmetrical molecules, the bond mo-
599
ments are not balanced and hence the resultant moment
is greater than zero. Magnitudes and directions of the
major bond moments (4) are given along with the
measured moment for the molecule as a whole. The
units are e. s. u., or debye units. The vectorial
additivity of these moments is quite evident. The
agreement between calculated and observed moments is
less close in the ortho and meta positions than in the
para position. Probably this is due to interaction be-
tween the two substituted groups which spreads them
apart thus causing a lower moment than would other-
wise be expected. This effect is more noticeable in the
ortho than in the para position because the substituted
groups are closer together in the ortho position.
Vectorial addition of bond moments becomes a con-
siderably more complex affair in the case of nonplanar
139 CALCULATED 3.44 CALCULATED 4.91 C A L C ~ L A T E O
1.3 OBSEIVED 3.4 OBSERVED 4.3 OBSERVED
Fig- 5. Dipole Moments of Som. Polar M o l e c u l ~
molecules. Vectors must then be resolved in three di-
mensions. Still further complications are introduced
by the possibility of rotation about single bonds. In
all cases, however, the general concept of vectorial addi-
tion of dipole moment vectors is valid. Values of a
number of bond moments are given in Table 2 for
reference.
Contributions of resonance to the dipole moment arise
in the manner shown in Figure 6. Five resonance
structures have been drawn. Structures a and b con-
tribute nothing to the total moment because they do
not represent a separation of charge. Structures c, d,
and e, however, do show a separation of charge and
hence set up a dipole moment. Now the actual struc-
ture of chlorobenzene is some combination of these five
structures with a and b predominating. The dipole
 JOURNAL OF CHEMICAL EDUCATION

TABLE 2 would expect, then, that the resonance structures would

Bond Moments (2) decrease the net moment of the aromatic halogen com-
pound. This is in agreement with the observed values
Bond Bond
(++I Moment (++I Momat in Table 3. In the case of the NOz compouuds, the
bond moment of the C-NO2 bond is directed from C to
H-C C-S NO*. But the effective moment set up by the reso-
H-N C=S
H-P C-F nance structures of the aromatic NOz compound is, as
H 4 C-CI shown in Figure 6, also directed from C to NOz. Thus
H-S C-Br in this case the vectorial sum of the moments is greater
C-N G I
Ca N-0 in the aromatic than in the aliphatic group, again as
C-0 N=O shown in Table 3.
C=O
TABLE 3
moment therefore will be the vector sum, properly Dipole Moments of Aliphatic and Aromatic Compounds
weighted, of the C C 1 bond and the moments of the po- XIR CHI CeHs
larized resonant structures.
A quantitative estimate of the effect of resonance H 0.00 0.00
CHs 0.00 0.41
may be had by an examination of Table 3 (5). If the OH 1.68 1.61
dipole moments of both the aromatic and aliphatic CI 1.87 1.55
I 1.60 1.30
compouuds shown in the tables were associated only CN 3.44 3.90
with the bond between the carbon and the substituted NO* 3.02 3.95
group, then we should expect very close agreement be-
tween the dipole moments of the aromatic and aliphatic MEASUREMENT OF DIELECTRIC CONSTANT
compounds. But the two values do not agree. The
The dipole moment of a material may be determined
observed moment of the aromatic halogen compound is
by measuring the dielectric constant of very dilute mix-
smaller than that of the aliphatic compound and the
tures of that material in a nonpolar medium such as
moment of the aromatic NOz compound is larger than
benzene. Since the dielectric constant of a liquid is
that of the aliphatic NOz compound. These differences simply the-ratio of the electrical capacity of a condenser
are due to resonance. That these differences are in
when empty to the capacity of the same condenser when
general agreement with vectorial addition of the dipole
filled with the liquid, dipole moments can be calculated
moments may be shown in the following manner. The
from measurements of capacity. Apparatus for meas-
direction of the C-C1 bond is known to be from C to C1
urement of the dielectric constant of liquids consists of
as shown in Figure 5. The moment caused by reso- a cell of some sort, a suitable bridge circuit, an oscilla-
nance, as shown in Figure 6, is directed from C1 to C or
tor, amplifier, anduull detector.
in the opposite direction to the bond moment. We
The cell generally used in this laboratory is shown in
Figure 7. It consists of an inner cylinder with a wolf-
ram (tungsten) wire fused through the walls as shown, a
second cylinder concentric with the first with a second
wolfram wire sealed in as shown, and an outer cylinder
with two openings for connecting a thermal control
bath. A silver plating solution is placed in the small
space between the inner and center cylinders so that the
surfaces are given an electrical conducting plating.
The two platings or electrodes so formed on the sur-
faces are separated by air when the cell is empty or by
the solution being measured when the cell is full.'
Electrical contact with the two electrodes is made by
means of the two wires sealed through the cylinder.
Although this cell is difficult to construct, it is very
practical in use. Water maintained a t a constant tem-
perature can be pumped continuously through the
jacket of the cell, hence the cell and its control bath may
be handled as a unit. Much simpler cells can he con-
structed without the outer jacket. In that case, how-
ever, the cell must he immersed in a bath for tempera-
ture control.
The electrical capacity of this cell when empty is about 100
micromicro farads. About 15 ec. of the liquid to be measured are
required for filling the cell.
NOVEMBER, 1950

All of the electrical equipment required for measure-

ment of the electrical capacity of the cell is available
commercially. It may also, of course, be constructed
in the laboratory. The bridge must be capable of
measuring capacities in the range of 10 to 1000 micro-
micro farads to an accuracy of about *O.l rnmf. In
this laboratory we use a conventional audio frequency
oscillator, usually set at 1000 cycles per second, to drive
a General Radio Co. capacitance bridge. As a null de-
tector we use a conventional audio amplifier feeding
into a 500 microampere meter. In operation the bridge
is balanced with and without the cell connected to it, TEMPERATURE
and the difference in the capacity required to balance
the bridge in the two eases is equal to the capacity of
the cell. Bridge balance is indicated by a zero reading
on the meter. With a little practice, one can balanre
. -1

/' '
CONTROL BATH

the bridge in a fewseconds. ELECTRODE

LEAD
The procedure for making dielectric constant meas-
urements in this laboratory is as follows. First, the
cell is cleaned with acetone and dried by a stream of air
pumped through a drying tube and then into the cell.
ELECTRODES
A rubber atomizer bulb is used as the pump. The cell FORMED B Y
capacity is measured and then the cell is filled with pure TEMPEATWE SlLVER PLATING
CONTROL BbTH ON INNER WALLS
benzene and measured again. These measurements INLET
are made to determine the tme capacity of the cell from
the following equation:

where Csis the capacity of the cell filled with the liquid, F 1. Cell for M-mmant of Dielstris Constant of Liquid.
C. is the capacity of the cell when empty, and CL is the
capacity due to leads connecting the cell to the bridge.
r is the dielectric constant of the liquid which, in the by weight of solute in solvent. An example of such a
case of benzene, is 2.268 a t 25'C. If the leads are plot for nitrobenzene is shown in Figure 8. This plot is
short, CL will be small and can often be neglected. If a straight line as long as very dilute solutions are meas-
C, is appreciable however, and if the dipole moment be- ured, but as the concentration is increased, the points
ing measured is small, then CL should always he sub- will depart from a straight line because of interaction of
tracted from the measured cell capacities before the di- the molecules.
electric constant is computed. CALCULATION OF DIPOLE MOMENTS
The cell is again dried as before. Dry air is pumped
through the cell until its measured air capacity is the The slope S of the plot of dielectric constant versus
same as the originally measured air capacity. This weight proportion of solute in solvent may be calculated
must always be used as the criterion of dryness if pre.. as the difference in dielectric constant divided by the
cise results are to be obtained. Finally, the liquid to difference in weight proportion between any two points
be measured is placed in the cell and measurements are on the curve. The slope of the plot shown in Figure 8
again made. Equation (2) is used to calculate the di- is thus 14.0. The dipole moment ( p ) of the solvent may
electric constant of the liquid. The atomizer bulb be calculated from the following equations.
and air drying tube are connected to the left-hand spout
in Figure 7 and the liquid to be placed in the cell is
sucked in through the right-hand spout. When used
for drying, the tube is connected to the right-hand spout
and a cap is placed over the left-hand spout. The
pressure of the air in the cell forces the cap up, but as
soon as the pressure drops, the cap seals off the spout.
Thus only dried air passes through the cell.
Samples containing various proportions of the ma-
terial whose dipole moment is to he determined are
made up with benzene or some other nonpolar liquid as
the solvent. Each of these samples is measured, and
the dielectric constant is plotted against the proportion
 JOURNAL OF CHEMICAL EDUCATION

bond refractivities are given in Table 4 (6, 9). The PO

value for nitrobenzene, for example, would be calcu-
lated in the following manner. In the CeH&TOBmole-
cule there are five C--H bonds, six Cay-C., bonds, one
N-C bond, one N-0 bond and one N=O bond.
+
Therefore Pa,= 5 X 1.7 . 6 .X. 2.7 , 1 X + +
. . 1.5 , -1 X
..
+
1.7 1 X 4.8 = 3217 cc.
DIPOLE MOMENTS AND MOLECULAR STRUCTURE
Information concerning the possibility of Zwitterion
ion formation in phenylazo-l-naphthylamine was de-
sired. Dipole moment measurements were therefore
made on l-naphthylamine and on 2- and 4phenylazo-l-
naphthylamine. The results of the measurements and
the structures of these three molecules are shown as a,
b, and c in Figure 9.
Azobenzene, because of its symmetry, hm no dipole
moment. It is somewhat surprising, therefore, to note
the comparative values of l-naphthylamine and 2- and
4-phenylazo-l-naphthylamine. If no resonance struc-
tures were possible, one would expect all three com-
pounds to have the same moment. The small differ-
ence between naphthylamine and 2-phenylazo-l-naph-
thylamine can be ascribed to usual resonance phenom-
ena, but the large moment of the para dye argues
greatly enhanced resonance effects. Resonance struc-
tures such as that shown a t d in the figure appear quite
plausible. This enhancement of resonance effects (or
Zwitterion formation) in the para position has been de-
(3)
scribed for several of the aso dyes by Bergmann and
Weizmann ( 1 ) .
If, as the dipole moment suggests, a larger number of
(4) resonant forms are probable in the para compounds,
then the para compounds must exist in a lower energy
d (-~P,)T e. s. u.
a = 0.0127 X (5) state than do the ortho compounds. Consequently, in
The symbols have the following meaning: a reaction in which both forms are made one would ex-
pect a greater percentage of para than ortho compound.
rr = dipole moment We have found this to be the case.
P = molar polarieation
Po = optical polmimtion In another problem, a compound analyred as CldIlo
M. = molecular weieht of ~olvent was synthesized in the laboratory and a question arose
o, - = density of so1;ent concerning its structure. Was it a ten-membered ring,
PI = densit? of solute
eI = dielectric constant of solvent
n, = index of refraction of solute
T = abdute temperature at which all measurements are TABLE 4
made Bond Refractivitim (9)
Equations (4) and (5) are given by Debye (4) and equa- Bond Rejraetiuity Bond Rejmetivitr
tion (3) was derived in this laboratory to replace the H-F 1.90 cc. C-C
graphical method of calculation described by Debye. H-0 1.88 N-N
In order to calculate the dipole moment from equa- H-N 1.87 N-0
H-C 1.70 -0
tions (3), (4), and (5), the index of refraction and den- H-8 4.77 SS
sity of the pure solute must be measured a t the same H-CI 6.67 CI-CI
temperature used for measurement of e (usually 25°C.). H-Br 9.17 CS
H-I 13.74 C-CI
Density values are, of course, relatively simple to ob- C=O 3.42 C-Br
tain, but measurements of the index of refraction, par- C-S 12.5 C-I
C=N 4.93 N-CI
ticularly of solids, are often d i c u l t to make. It is N=O 4.80 C=C
possible, however, to eliminate measurement of n by C-F 1.60 C=C
calculating Pa directly from tables of bond refractivities. G-0 1.46 C,-C,.
C-N 1.45 C,-c,
To within the accuracy usually required in Po, the bond
refractivities are additive and in most cases are known Benzene bond
6 Naphthalene bond
sufficiently accurately. For purposes of reference,
NOVEMBER, 1950 603

i.e., a symmetrical structure? If it was a symmetrical

structure, it should have a dipole moment of zero.
Measurements showed the molecule to have a moment
of 2.0 0.1 debye units. Obviously, the molecule
could not be symmetrical and could not, therefore, be a
ten-membered ring.
We wished to know, in another case, the position of
the central hydrogen atom in the compound 4methyl
diazo amino benzene illustrated in Figure 1Oa. Because
of the complexity of this molecule, an interpretation of
its structure in t e r n of its dipole moment is di5cult to
make. The two compounds shown in Figure l o b and c
were therefore synthesized2 and the dipole moments of
all three compounds were measured. The dipole mo- A = 1.03
ments are shown in the figure. Withm the limits of ac-
curacy, the dipole moments of compounds a and c are Firrun 10
identical, but the dipole moment of compound b is rad-
ically different. We must conclude from this that the work done by Mr. G. W. Wright in making most of the
position of the central hydrogen atom in compound a is measurements reported in this paper and to Dr. L. T.
the same as the position of the central CHa group - - in Hallett for criticism of the manuscript.
compound c. LITERATURE CITED
These are a few of the cases which have been studied
(1) BERGMANN AND WEIZMANN, T ~ a mF. a ~ a d n ySoc., 32,1318.
in this laboratory. The simpler molecules might have
( 2 ) BERNTBSEN,A,, AND J. J. SUDBOBOUGB, "Tex&Book of Or-
been used as illustrations, but these can be found in ganic Chemistry," D. Van Nostrand, New York, 1941, p.
any good study of the problem (3, 4, 6). These more 1284.
complex examples have been cited to indicate that this (3) BnANcn AND CALVIN,"The Theory of Organic Chemistry,"
sort of information is useful in the solution of many com- Prentice-Hall, Inc., New York, 1941, chap. V.
plex problems of chemistry. (4) DEBYE,P., "Polar Molecules," Dover Publication, New
York, 1945.
(5) DENBIGH, K. G., Tram. Faraday Soc., 36,936.
(6) LEFEVRE. R. J. W., "Dipole Moments," Methuen and Co.
The author wishes to express his appreciation for the LM., Landon, 1948.
(7) PAULING, L., "The Nature of the Chemical Bond," Cornell
Univ. Press. Ithaort. New York. 1939. o.64.
'These syntheses were carried out by C. Benhrooke who sug-
gested a study of this particular problem, and by E. Aiken.