Haile Solomon Dielektrizittskonstante 25.06.

2015
Ida Thudium

1 Theoretical Background
The purpose of this experiment is to find the dipole moment of 2-butanone. For that the dielectric
constant r and the refractive index n in different solutions with 2-butanone solved in cyclohexane will
be measured.
With spectroscopy it is possible to measure interactions of electromagnetic radiation with matter. The
dielectric property is a specific property of a material, which depends on a permanent or induced
dipole.

1.1 Dipoles and electric fields

A dipole affects the electric field if electromagnetic radiation hits the material. The charges are
influenced by the electric field. For this field there is a capacitor. The electric field is defined as
followed:

| |

And the capacity is defined as:

As a following the surface charge density is defined with the following equation:

With for the electric field constant.

If there is a non-conductive material and a constant voltage between the two capacitor plates you can
measure a current. This means the value of increases, it is named with D. As a result you will get
the following equation:

The proportionally factor is called relative permittivity, it is used as a measure for the polarizability
of matter.
In the dielectric there are no mobile charge carriers, but existing or induced dipoles can be aligned.
The electrical polarization is defined as followed:

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Haile Solomon Dielektrizittskonstante 25.06.2015
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1.2 Types of polarization

There are mainly two types of polarization, the induced dipole moment and orientation
polarization.
1.2.1 Induced dipole moment
The electrons are influenced by the electric field, because of that they are shifted relatively to the
positive core. It is proportional to the local electric field strength, which is described by the
polarizability . It shows how easy the electric charges can be moved within a molecule. There is an
equation by Clausius and Mosotti which describes the polarizability by using .They called it PV and
defined it as followed:

1.2.2 Orientation polarization

Orientation polarization you have for molecules with a permanent dipole moment in an electric field.
Without an electric field you have no orientation polarization. In the electric field the permanent
dipoles want to orientate themselves. The thermal motion acts against this orientation. That shows that
there is temperature dependence. With the Boltzman statistics the orientation polarization is described
as:

This is combined with the Clausius-Mosotti equation, than the polarization can be described like that:

( )

1.3 Frequency dependence of the DK

At low frequencies the polarization can follow all phase shifts. At higher frequencies not all process
are able to follow. At the end the relative DK approaches its vacuum value of 1.
The measured graph shows a dependence of the refractive index and the relative permittivity.

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2 EVALUATION

2.1 Evaluation after Hedestrand

With this procedure ,the mixer dielectric constant and the mixer density are plotted against the
molar fraction . Therefor the analyzed substances have to be dissolved into an unploar solvent.The
intermolecular interaction can be neglected if the refraction index and the dielectrix constant is being
measured at high dilution and then extrapolated to a concentration of zero.

(1)

(2)

The indices B and C represent Cyclohexan and Butanon and the gradients are represented by a and
b. With the law of mixtures the whole polarization and the molar refraction can be broken
down to its two components B and C. For Butanon-2 it means:

(3)

(4)

If is approached to zero, the molar polarization of the analyzed substance can be determined by:

( ) (5)
( )

With the approximated values, the orientation polarization can be determined by:

( ) (6)

To get the molar refraction of Butanon , the molar refractions of the pure solvent and the
mixture have to be calculated at first:

(7)

(8)

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If has been calculated by formula (8) it can be put into formula (6) to determine the dipole moment
with (9) or (10):

(9)

Formula (10) is followed by (9) if the constants k = , ,

and the temperature of are put in:

(10)

At first has to be determined by the scale divisions x read of the measuring device with the help of
DK1:

(DK1) (11)

The density can be measured by weighing the mass of an empty pycnometer and the masses
of the pycnometers filled with cyclohexan and butanon . In combination with the volumes of the

different pycnometers the densities can be calculated by .

In the following diagrams the dielectric constants and the density are plotted against the molar
fraction :

Linear Regression for Data1_B:

Y=A+B*X
Parameter Value Error
--------------------------------------------------
A 2,08464 0,00343
B 8,94776 0,0558
--------------------------------------------------
R SD N P
--------------------------------------------------
0,99992 0,00459 6 <0.0001
--------------------------------------------------

Illustration 2.1 plotted against

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Linear Regression for Data1_B:

Y=A+B*X
Parameter Value Error
----------------------------------------------------
A 772,24143 4,51028
B 380,90254 88,21701
----------------------------------------------------
R SD N P
----------------------------------------------------
0,95032 5,47683 4 0,0496
----------------------------------------------------

Illustration 2.2 plotted against

The following values and errors have been determined by the diagrams:

Value Error
a 8,94776 0,0558
2,08464 0,00343
b 380,90254 88,21701
772,24143 4,51028
Chart 2.1

Because of the big differences of two measurement points, these two values have been masked.

These values can now be used to calculate the molar polarization ( ) with formula (5):

( )
( )

With the molar polarisation ( ) the orientation polarization has to be calculated, therefor the
molar fraction has to be determined. At first and are needed.

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(Excel appendix) :

(12)

To determine the average value of is needed:

( )

( )

At last the dipol moment is calculated by (10):

2.1.1 ERROR DISCUSSION:

To determine the error in our calculation we use the following formula:

( ) ( ) (13)

To calculate the error of , the error of is needed. As stated in (6), is composed of ( ) and
or .

( ) ( ) ( ) ( ) ( ) (14)

The single errors are calculated by:

( )

( )
( )
( )
( ) ( )

( ) ( )
( ) ( )
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The errors of the single values are stated in the cart related to the first to diagrams:

( ) ( ) ( ) ( )
( )
( ) ( ) ( ) ( )

The standard deviation of :

( ) ( ())
( )

For the error rate of orientation polarization , the errors of and have to be included:

( ) ( ) ( )

With the help of the error oft he orientation polarization the error oft he dipole moment can be
calculated:

( ) ( ) ( ) ( )

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2.2 Evaluation after Guggenheim

For the indication of concentration the method of mass fraction is used which is equal to the molar
fraction. The dipole moment after Guggenheim can be defined by:

( )
( )

with.
( ) ( )
For the determination of

( ) ( ) ( )

the mass fractions each are plotted against

( )

and

( )

and an extrapolation with 0 is performed.

Illustration 2.3 plotted against

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Out of the plot via the y-intercept of the regression line the value for ( ) can be

determined:

( )

Because of the great stray of the first values, they have been masked.

Illustration 2.4 plotted against

As in the last diagram, the value of ( ) can also obtained the same way:

( )

Those values result into:

( ) ( ) ( )

( )

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2.3 Evaluation after Smith

Unlike the two methods already mentioned, the calculation of the dipole moment after Smith only
needs the dielectric constant and the refractive index of the solvent. With those two values the dipole
moment can be determined by:

( )
( )

The represents the gradients of line of best fit from illustration 2.5 and the one from illustration
2.6:

resulting in a dipole moment:

( )

( )

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Illustration 2.5 plotted against

Illustration 2.6 plotted against

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2.4 Evaluation after Onsager

In contrast to the method of Smith, the dipole can also be calculated at high pressures, since the mutual
polarization of Interacting molecules are taken into account. The additional polarization leads to a
creation of an electric field, which points into the same direction as the induced dipole contributing to
the total field strength.

The dipole moment is calculated by:

( )( )
( )
With:

and and

Follows:

( ) ( )

( )

The evaluation method after Onsager serves to determine the dipole moment of pure fluids.

3. Comparison of the results

Evaluation method Dipole moment [Cm]

Hedestrand

Guggenheim
Smith
Onsager
Literaturwert

The results show that the method of Guggenheim created the most accurate value, with method of
Hedestrand the second, Smith the third and the Onsager as the least accurate one.
During the evaluation after Hedestrand the complexity of the process concluded us to guess that
because of the use of the densities and masses of the fluids, it would be more prone to errors than the
Smith method, because it doesnt rely on the density. The Onsager method cant be evaluated because
of the only use of literature values.
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Molenbrche Literaturwerte:
xB VB MC 0,08416 T 293,15
0,02 0,84 MB 0,07211 0 8,85E-12
0,04 1,72 C 780 k 1,38E-23
0,06 2,63 B 810 NL 6,02E+23
0,08 3,59 VC = 50 ml nB 1,379
0,1 4,58 rB 18,50

Kolben leer mit C mit C & B mC mB

Lsg. 1 35,6564 74,5424 75,3362 38,886 0,7938
Lsg. 2 38,468 77,3551 78,9455 38,8871 1,5094
Lsg. 3 38,0568 76,621 78,6927 38,5642 2,0717
Lsg. 4 42,2386 80,8064 83,6861 38,5678 2,8797
Lsg. 5 42,0625 80,676 84,3774 38,6135 3,7014
reines C 38,1995 79,9241 41,7246

Pyknometer leer [g] voll [g] m [g] [g/l] V [ml]

Lsg. 1 31,3991 70,7623 39,3632 775,400 0,050765
Lsg. 2 33,5332 73,7055 40,1723 770,189 0,052159
Lsg. 3 30,4363 70,3761 39,9398 798,796 0,05
Lsg. 4 30,6934 70,7658 40,0724 801,448 0,05
Lsg. 5 30,3172 69,0758 38,7586 775,172 0,05
reines C 31,5314 70,2923 38,7609 775,218 0,05

xB xC B Skalenteile BC nBC
Lsg. 1 0,0233 0,9767 0,020005 426 2,2896 1,4250
Lsg. 2 0,0456 0,9544 0,039291 558 2,4865 1,4238
Lsg. 3 0,0590 0,9410 0,050982 638 2,6059 1,4230
Lsg. 4 0,0802 0,9198 0,069478 766 2,7969 1,4215
Lsg. 5 0,1006 0,8994 0,087473 896 2,9908 1,4205
reines C 0,0000 1,0000 0 291 2,0882 1,4260

RBC RB BC-C/B BC-C nBC-nC/B nBC-nC

Lsg. 1 2,77E-05 2,111E-05 10,068 0,201 -0,1425 -0,0029
Lsg. 2 2,77E-05 2,504E-05 10,139 0,398 -0,1596 -0,0063
Lsg. 3 2,66E-05 7,238E-06 10,155 0,518 -0,1676 -0,0085
Lsg. 4 2,64E-05 9,537E-06 10,200 0,709 -0,1844 -0,0128
Lsg. 5 2,71E-05 2,077E-05 10,319 0,903 -0,1790 -0,0157
reines C 2,78E-05 0

Eichgerade DK 1: y=1,492*10-3x+1,654 (y: DK; x: Skalenteile)

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Eichgerade DK 2: y=2,007*10 x+0,82558 (y: DK; x: Skalenteile)

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