11.3.2 DrP OL E ,10 :\lE '.

\T
OF A~ OR G _-\...'ilC :'.\lOLEC
Cl..L
_.\C ET 0:'1 -E

l. ~T RO Dt :C TI O: \:

A mo lec ule in \\h ich the cen

ter of neg ati \·e cha rge is dis
pos i ti\·e cha rge is said 10 ha\ pla ced fro m 1he cen ter of
e an ele ctri c di pol e m om ent
like Ca rbo n tetr ach lori de CC _ In a hig h s~m me tric molc"Cule
L and ben zen e C J---l.~- the Cen
cha rge s \\ ill coi nci de and the ter of pos itiw and neg ati \·e
molec ule has no d ipo le mo me
as~ mm etri c mo lec ule s like CH nt as mentioned e:irl ier. In
C1 3 and ace to ne_ the re is a
dip ole mo ment per n10lecule_
C o nsi der a mo lec ule that has
a per ma nen t dip ole mo me nt
app lied ele ctri c field _ The mo p e\·en in the abs enc e of :in
me nts on dif fer ent mo lec u les
ran dom in the abs enc e of in the material are orie nted :it
the field . Th is ran dom o rien tati on aris
agi ta tion . \\'h en an elec tric es due to themrnl
field is app lied . it tr ies to :ilig
o f the field and th is is o ppo sed n the mo ments in the di...-n:t ion
b~ th erm al ene rg~ .

Th e e ner g~ o f a d ipole in an.

elec tric field is

- p. E 1c...i1 = -pE 1oc.11 cosO (ll. S.2 .1 )

\\ her e 0 is the ang le bet \, een
p and E i.., 3'·

Th e pro babilit~ tha t a dip ole

is o rien ted :it :in ang k 0 10 the
to the Bol tz.ma n fac tor exp electric fi eld is proport ional
[-{ - pE•~,~ cos 0 k TI and tJ1e
m o lec ule in the d irec tion o f the ave rag e dipole mo ment per
local ele ctri c fiel d is

p3 , = 2rc j"pco s0 exp ( pEi.., -:,1 cos

0 kTI sin 0d0 2:tJ exp ( pE1..-=1 cos 0 kT) sin0
0
(I d0
Wh en pEh-,,1' kT << I. the abo
w inte gra l is nea rly equ al to

[i / 3kT] Ei..--=1 = £o a..,.,,,, Ek=l

Uon a1 is cal led the orie nta tion al con
trib utio n to the pob .riz abi lity .
 Fo r a molecule \\ ith a pem1anent dipole nwment p. the tc1 tal polariz.ab ili t\ a ,s the: ,
11111
o f the electron ic and o rientati0nal polarisabili1 ies ·

( 11.5 :2 3)
So

(11. 5 2.--l l
\\ here >i is the number of mo lecules per uni t \·o lu me .

The o rientati onal contribut ion to the po larizability o ften out\,ei g.hs the electron ic
cont ributi o n. The dielectric constant is th en strong ly depend en t on tem pera ture and
inc reases as the tem perature is reduced .

If \\ e ha,·e a non -polar liquid G in \\ h ic h a po la r liquid H is di ssolved 111 small

quan tities. the dielectric constant o f the mixture sati s fies the relation

(£, - I )! (£,+ 2) = (1 /3 ) [N G U.,1 G + NH(PH" /3 eokT)] (11. 5.2.5)

Here "e have neglected the electronic contribution to the polarizabilit y of the mo lecul e H
in re la ti o n to its orien tational contribution . NG a nd NH are respectiw ly the num ber o f
m o lec ule s per cubic meter of liquid G a nd liquid H in the mixture . By adding small
q ua ntities o f liquid H to liquid G and varyin g th e rel a tive concentratio n of G and H one
can p lot th e dielectri(; con stant of the mixture as a function of the concentratio n NH. For
low conce ntrati ons of liquid H (i.e. a few percent) th e va riati on will be linear. From this
pl o t o ne can calcu late the dipole moment PH o f m o lecu le H.

O ne can a lso measure the temperature , ·a ri ati o n of the dielectric con stant fo r a mixture
w ith a given concentratio n of H in G . A plot of the di e lectric constant as a fun ction of
Irr is used to get the dipole moment PH
The dielectric constant of any materia l is a function of frequency. The electronic
motions a re characterize d by frequencies in the ultra-v iolet. The vibrational motions of
the atom s in the molecule are in the infra-red region. The orientational motions o f
m o lec ular groups are in the far infra red and microwave region. As the frequenc y is
v aried . the dielectric constant varies as shown in Figure 11.5.2. 1.

Nea r th e characteristi c frequencies of orientatio n. v ibration and electron ic moti ons. the
dielectric constant goes through a maximum and a minimum . The region of frequen cy
between the maximum and the neighboring m inimum (the region in which the dielectri c
co n sta nt decreases) is ca lled the region of anomal o us dispersion .

1~ 7
 To calc ulat e the dipo le m o men t
one sho uld wor k at freq uen cies
orie ntat ion freq uen cy. A freq uen low com pare d to th e
cy up to a few hun dred kilo -her tz
in som e mat erial s one may see a is nor mal ly OK th o ugh
no ti cea ble disp ersi on in this regio
n.

Ori enta tion

Vib rati on
Elec tron ic

i
w

0 Freq uen cy

Figu re 11.5 .2. 1 Var iati o n of diel

ectr ic co nsta nt of a material with
freq uen cy
sho w in g th e orie ntat i o na l, v ibration
al and e lect roni c con trib utio ns
2. APP AR AT US RE QU IRE D

Cap acit anc e mea suri ng circ uit , cyli

ndri cal capa cita nce in a grad uate
mea sure to thre e dec ima l plac d jar, a DM M to
es in the DC 2 V rang e and
com pos itio n of acet one and ben ze mix ture s of different
ne in was h bott les.

3. DIPOLE MOMENT OF AC ETO

NE : EXP ERI ME NT
Ace tone is a mol ecu le that has a
perm ane nt dipo le mom ent. Its pola
freq uen cies aris es mai nly from the ri za bilit y at low
orie ntat iona l con trib utio n of the dipo
the dipo le mom ent of the mol ecu le. To mea sure
le, mix I 00 mill ilite rs of Ben zen
acet one . For exa mpl e we can prep e and v Ac mill ilite rs of
are thre e mix ture s, with VAc =I0 ,
The se mix ture s hav e to be stor ed in 15 and 20 mill ilite rs.
an airt igh t bott le so that no wat er
by the mix ture s. is ads orb ed

)88
 T he dielectric constant or eac h mi x ture is meas ured fo ll ow in g th e p rocedu re de sc ri bed
wi th ben ze ne .

Le t th e j th mi xture co ntain I 00 millilit e rs o f benze ne and VjA C millilite rs o f Aceto ne .

Let th e di e lec tri c co nstant o f thi s mi x ture be Emj• T he n we ca lc ul ate th e va lu e of

( II. 5 .2 .5)

fo r th is mi xture j . Here En is th e d ie lectr ic consta nt of be nzene, a nd ErnJ is th e d ie lectri c

constant of th ej th m ixt ure . T hi s va lu e KJ sho uld be th e sa me fo r a ll th e mi x ture s j. Take
th e average va lue K av· T he n

( 11.5 .2 .6)

w here NAc is th e number o f m o lec ul es per mete r3 o f pure Aceto ne, k is th e Bo ltz m a n
co nsta nt , T is th e abso lute te mperatur e .

Sa mp le readin gs are g iven be low :

Table 11. 5.2. 1

D ipo le m o m ent o f Aceto ne

DC Vo ltage due to leads Vo = 0.020 V

DC Vo ltage w ith th e ca pac ito r in a ir: V a,r 0.4 12 V
T hree m ix tures we re made by m ix in g I 0, 15 and 20 ml of Ace to ne (AC) w ith I 00 ml of
13cnzene (B) T he DC Vo lt ages fo r d iffere nt fillin gs in ml are g ive n.

Mixture 1 M ixture 2 Mixture 3

100C6H6+ 10 100C6H6+ 15 Acetone 100C6H6+20 Acetone
Acetone
V= 427+8.32 m V= 447 +9.89m V=444+13 .46m
milliliters V inmV V inmV VinmV
0 427 447 444
10 512 547 580
20 591 642 713
30 680 742 850
40 755 845 980
50 843 945 1120
60 928 1040 1250
70 1010 1135 1390
80 1088 1242 1520

189

)
 As in th e pre v io u s c ha p
te r a g rap h is dra w n bet we
and a stra i ght lin e is fitt e n th e vo lt age a nd mi llil
ed . T h e fitt ed equ at io n it ers o f liqu i d
row o f th e ta bl e . fo r th e s trn ig ht lin e is g
Fro m th e se equ nti o ns th ive n in th e th ird
eva lu ate d as d e sc rib e d in e d ie lec tri c co ns ta nt o f
th e pre v io us chnpte r. th e mi xtu res arc

T he di e lec tri c co n sta nt s

o f vn ri o us mi xtu res nncl
are giv en in Ta bl e ll. 8.3 th e d ie lec tri c c o ns tnnt o
.2 a nd th e va lu es o f K arc g f p ure be nze ne
ive n in th e la s t c o lum n .

Ta ble 11.5 .2 .2

Liq uid E:, (E:,-1)/(E:, +2) K

Be nze ne 2.1 0.2 683
Mix1 2.95 0.3 939 1.6 5
Mix 2 3.36 0.4 403 1.5 9
Mix 3 4.17 0.5138 1.7 4
Average K 1.6 6

Th e ave rag e v a lue o f K

= 1.66 .
T he mo l ecu lar w e igh t of
Ac eto ne (C 3 H 60) is 58 g.
num ber of ace ton e mo lec Its den sit y is 0.7 92 gle e.
ul e s N Ac pe r m 3 is So th e

N Ac = (6 .02 2x 10 23 x 0.7
92/58)x10 6 = 8.4 9x l0 27/m 3
(ll. 5 .2. 7)
Dip ole mo me nt of ace ton
e mo lec ule is

P = ((K /N Ac) (9£o kT )) 1/2

(Il. 5.2. 8)
He re £o = 8.8 5x l0· fd/ m
12

k = 1.3 6x 10- 23 J/K elv in

T = 300 K

Su bst itu tin g for the v a rio

us qua nti ties we get

p = 8.0 x 10- 30 cou lom b me ter.

Fro m th e lite rat ure th e e
lec tri ca l dip ole mo me nt o
De b ye = 3.3 4x l 0· 30 co ul f ace to ne m o lec ul e is 2 .88
o mb m ete r) o r 9.6 x 10·30 cou De bye ( I
l o mb m ete r.

190
 The experiment is intended to show lhe orde,· '!{Jdipole mom e nt valu es . in
molecules. The electronic charge is of the order of IO Coulomhs and lh e relative
displacement of the CG of positive charge relative lo CG of negative charge is o f th e
11
onler of a fraction of an Angstrom ie of the onler of I 0- 111. So lhe dipole moment
.
I mete,.
o f a molecule is of the order of IO . 19 x IO · " = I o -Jo cou I 0111:, .

CAUTION: NEVER USE WATER WITII THE

CYLINDRICAL CAPACITOR

Questions:

I. In a cylindrical capacitor will the capacitance increase if the ratio r 2/ r 1 is

increased? Here r2 is the radius of the outer cylinder and r 1 the radius of the inn er
cylinder.

2. Can yo u have a liquid for which the dielectric constant at very low frequencie s is
less than I ?

3. Can you think of a way of controlling the level of a liquid using its dielectric
constant?

4. Derive the formula involving p and K (Equation 11.8.3 .5).

5. Water has a dielectric constant of 80. Do you expect the water mol ec ule to have
a large electric dipole moment?

19 1