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Dipole Moment

(Friday, 28. November 2008) I. Summary The dipole moment of some polar molecules in non-polar solvents is determined. To do so, relative permittivity and refractive indices have to be measured. The relation between macroscopic quantities and molecular (microscopic) properties are discussed.

II. Theory 1. Definition of the dipole moment A system that contains two separated charges of opposite sign, q1 = q and q2 = -q is called an electrical dipole. This is defined quantitatively by the dipole moment :

= q(r2 " r1 ) = qr
! r1 and r2 are the vectors that define the position of the two charges in the space.
!

(1)

Figure 1: Definition of the dipole moment as a vectorial property The dipole moment is thus a vectorial property. For any distribution of negative and positive point charges qi the dipole moment is:

= " qi ri
i

(2)

where ri are the positions of the charges qi. In the case of a continuous charge distribution, the dipole moment becomes

# r"(r)dV
1

(3)

r Here, r are position vectors, "( r ) is the charge distribution, and dV is a volume element. The sign of the charges has thereby always to be considered. The dipole moment of the electrical dipole moment of a molecule is the sum of the contributions of the positively charged nuclei and the r r r electron distribution: = + + " . The nuclei can in good approximation be ! negatively charged ! N r r r treated as point charges: + is thus given by + = " Z ieRi where Zi is the nuclear charge of nucleus I =1 r Ni, e is the elementary charge, and Ri is the position vector of this nucleus. For the determination of ! r the electronic part " the electron distribution has to be known. This can be obtained from quantum ! chemical calculations. In the case ! neutral molecules, the dipole moment is independent of the of chosen coordinate system. This is, however, not true for ions. ! ! According to general convention, the dipole moment points from the centre of the negative charge

distribution to the centre of the positive one. If the two centres do not coincide the molecule has a permanent dipole moment. Its existence is strongly related to the symmetry properties of a molecule. Molecules with a symmetry centre like benzene, acetylene, or nitrogen, for instance, have no permanent dipole moment. In the case of HCl, however, the centres of the two charge distributions do not coincide. In the SI system, the unit of the electrical dipole moment is Cm. Since these units produce very small numbers, the unit Debye (1D = 3.3356410-30 Cm) had been introduced in honour of the discoverer of the dipole moment, Peter Debye (1911-1912 Professor of theoretical physics, University of Zurich). Two elementary charges (e = 1.60210-19 C) of opposite sign placed at a distance of 1.28 * 10 -10 m, i.e. the bond length of the HCl molecule, give rise to a dipole moment of 6.14 D. This corresponds to a purely electrostatic model for the ionic HCl structure. In practice, however, only a dipole moment of 1.08 D is found. The molecule has thus only partial ionic character. For the description of partially ionic chemical bonds the ionic character X has been introduced:
X=

(measured) "100% (calculated)

(4)

In the case of HCl X is 17.6%. Experimental dipole moments provide information about the electron distribution in a molecule. Based on a vast amount of experimental data, group dipole ! moments have been assigned to functional groups in organic chemistry. By means of these values, dipole moments of new substances of known structure can be estimated via simple vector addition. Large deviations from the measured dipole moment indicate that either the structure of the molecule is inappropriate or that the molecule exhibits strong inductive or mesomeric effects. In this experiment dipole moments of some polar molecules in non-polar solvents are measured and discussed. This is practically done by measuring relative permittivity and refractive indices of solutions and pure solvents. The relation between theses two macroscopic properties and the molecular dipole moment is discussed in the following.

2. Relative permittivity, polarization, and polarizability Between two charged plates of a condenser is an electrical field. If the distance between the two plates is much smaller than the surface of the plates, the electrical field between the two plates is homogeneous except in the border regions (Figure 1). The electrical field strength E0 is given by 2

E 0 = 4 "q /S = 4 "# 0

(5)

! !

where " 0 = q /S denotes the surface charge density of one condenser plate (S = surface, q = charge on one plate). The voltage U0 between the two plates is proportional to the charge q:

Figure 1: Electrical field in a condenser


q = C0 " U 0

(5)

The proportionality factor C0 is called the capacity of the condenser. Between C0 and the field strength E0 the following relation is valid:
C0 = q /U 0 = q /(E 0 " d)

(6)

C0 is thus proportional to 1/E0 providing q and d are constant.


!

2.1. Experimental observation Compared to the voltage U0 that is measured between two condenser plate in vacuum the voltage is reduced to a smaller U when the condenser is filled with matter: U = U0/, E = E0/, and thus C = C0 (7)

with > 1. is the so-called static relative permittivity of the filled in material (dielectric) and is a material constant.

2.2. Explanation of this observation


r r In order to explain this behaviour the polarization P of a dielectric in a field E 0 is introduced. It is defined as follows

r r r r P = "0 ( E 0 # E ) = "0 (" #1) E

!
3

(8)

r r r and is a vectorial quantity. E 0 , E , and P are parallel oriented. Inserting (5) into (8) one gets the scalar relation

E=

(" 0 # P) def " ! ! = $0 $0

(9)

The electrical field E with a dielectric can thus be described as the field in vacuum. Its strength does not correspond to the surface charge density " 0 anymore but to a reduced density ( = (0 P)). r ! Polarization can thus be regarded as a surface charge density that is induced by field E 0 on the interface between dielectric and condenser plates. This induced charge density partially compensates " 0 because these charges have opposite sign. The so-called free surface charges are ! caused by three processes, which arise at the molecular level under the influence of an electric field. ! The observed polarization P can be regarded as being the sum of three contributions:
! P=P +P +P D E

(10)

Electronic polarization PE : It is found in all atoms and molecules. It is caused by the fact that the centres of the charges of the nuclei and the electrons are pulled in different directions in an external field.
!

Distortion polarization PD : This contribution is found in all polar molecules and is caused by changes in bond lengths and angles.
! PD and PE are combined to the so-called displacement polarization. It is thus caused through distortion of a molecule in an external electric field E. This causes an induced molecular dipole moment i . As long as the external field is not too strong, we can assume ! !

i = "E

(11)

! The proportionality factor is the polarizability. It indicates how easy a molecule can be distorted. In liquid solutions the induced dipole moment i is always oriented in direction of the external field.

Orientation polarization P : ! r P is only found in polar molecules with a permanent dipole moment 0 . It is caused by a partial alignment of the molecular dipole moment into the direction of the external field. In contrast to PD and PE , P varies strongly with temperature since the thermal motion is opposite to the alignment. !

! ! r In an external electric field, polar molecules have thus a total dipole moment according to ! ! r r r = 0 + i ! !

(12)

Our model of a dielectric between two charged condenser plates can now be sketched as follows +. It explains the free surface + charges q at the dielectric boundary surface S. P can then be written as: + + q'"d q'"d (13) P = q' /S = = S"d V (Figure 2). We hereby denote a molecular dipole moment by

Figure 2: Simple model of a dielectric P can be regarded as the electrical moment per unit volume of the dielectric, which due to the r molecular dipole moments i corresponds to the vector sum
1 l r P = " j V j=1 !
N

(14)

where Nl denotes the number of molecular dipole moments in volume V. This equation provides an r interpretation of the macroscopic property P in terms of molecular (microscopic) properties.

3. The Debye equation Debye developed 1912 a theory for the relation between the polarizability , the permanent dipole moment 0 and the relative permittivity of a substance. He found the following formula:
2 " #1 M N L & 0 ) = (% + + " + 2 $ 3"0 ' 3kT *

(15)

where M denotes the mol weight, the density, NL Avogadros number, and 0 the permanent dipole moment. The first term in parenthesis corresponds to the distortion polarization and the ! second term to the orientation polarization. One notes that the latter contribution becomes smaller with rising temperature, a consequence of thermal motion. This so-called Debye equation (15) neglects polar interactions of dipoles with their surrounding. It is therefore valid only for diluted 5

solutions of polar substances in non-polar solvents and for polar gases at pressures smaller than 1 atm. The Debye equation is the basic equation for the determination of molecular dipole moments in non-polar solvents. It order to apply it, however, polarizabilites of solvent and solute molecules have to be known. To determine these quantities, the refractive indices of solvent and solute molecules have to be measured.

4. Dispersion of the polarizability and the relation between and n 4.1. Dispersion of the polarization Dispersion generally means the frequency dependence of a physical quantity. The displacement of charge in a molecule due to an external field causes an induced dipole moment i = "E i . This effect, as well as the orientation of the permanent dipole moments, is achieved in a finite time. The same is valid for the reverse case, namely if the polarizing field is switched off and the molecules return into their non-polarized disordered initial state. The so-called relaxation time indicates how much time is needed until the polarization effects are ! reduced to 1/e after the external field has been switched off. Typical relaxation times of different polarizations are listed in Table 1. P obviously depends on the viscosity of the medium. polarization
PE PA P P

size of molecule

medium

[sec] 10-15 10-12-10-14 10-12 10-10-10-11 10-6 up to hours

frequency UV IR far IR microwaves radio frequencies

! ! ! !

small large

P P

gas solution, low viscosity solution, high viscosity glasses

! !

Table 1: Relaxation times at different frequencies and in different media The Debye theory is only valid if the polarizing electrical field changes slowly enough such that polarization and orientation of the molecules are always in equilibrium with the field. This condition is fulfilled with certainty in a static field or in solutions of low viscosity. Also, an alternating radiation field with a frequency of 106 Hz fulfils this condition since the relaxation time is much smaller than 1 s as seen in Table 1. From frequencies larger than 1010 Hz also the atomic polarization disappears (see Figure 3) and at frequencies higher than ca. 1014 Hz, only electronic polarization is left. P and thus also depend on the frequency and the contribution of electronic polarization can be determined by measuring at light frequencies of 4 to 81014 Hz. Figure 3 depicts schematically the discussed dispersion of the polarization.

Figure 3: The dispersion of polarization

4.2. The relation between n and From Maxwells theory of electromagnetic waves follows an expression for the phase velocity of a light wave in a medium with relative permittivity and a magnetic susceptibility m:

"=

c # $ m

(16)

where c is the speed of light in vacuum. The refractive index n of this medium is defined by:

n=

sin " c = sin # $

(17)

n is thus always 1.
!

= angle of incidence = angle of refractive = speed of light in medium

Figure 4: Refraction of light 7

For many organic substances m deviates only very slightly from 1, we can therefore write in good approximation:

"=
or
!

c #

(18)

n2 = "

(19)

The relative permittivity corresponds thus to the square of the refractive index n. Its magnitude and frequency dependence are a measure for the achievable electron polarization and its relaxation time.

4.3. The Guggenheim approximation For a completely independent determination of the polarizability in (15) the contribution of distortion polarization should be determined. This is however difficult to do. The Guggenheim approximation 2,3 allows approximate calculation of dipole moments of polar molecules in nonr polar solvents. It is based on the Debye equation and makes the determination of 0 possible solely by measuring and n2. Hereby, it is assumed that the distortion polarization of a molecule is proportional to its molar volume. The Guggenheim approximation reads
2 0 =

27kT 1 "0 $ M 2 $ (b" % bn ) NL #1 ("1 + 2)(n D1 + 2)

(20)

with
! b" = d" dw 2

and

bn =

2 dn D dw 2

(21)

The physical properties of the pure solvent are labelled with 1 and those of the dissolved substance with 2. nD is the refractive index at the frequency of the sodium D-line and w2 = m2 / (m1 + m2) is ! the weight fraction of the dissolved substance. The obtained experimental data is analyzed ! according to this Guggenheim equation. To do so, one needs the density (1), the relative permittivity (1) and the refractive index (nD1) of the pure solvent. The slopes b! and bn are 2 obtained by plotting and n D against the weight fraction 2.

III. Experimental part Dipole- and refractometer needed for the experiment have to be kept very accurately at the same constant temperature.

1. The dipole meter In this part of the experiment, we want to determine the relative permittivity at low frequencies, i.e. in the region of radio waves (~106 Hz). In this spectral region, all contributions to the polarizability are effective (see Fig 3). To do so, we use a dipole meter, which consists of a resonant circuit that oscillates at its eigenfrequency:

" =

1 2!

1 LC

(22)

The eigenfrequency is measured with a frequency counter. Filling the capacitor with a liquid changes C according to (7): C = C0 We can thus rewrite Eqn. 22 to

"=

1 2#

1 LC0$

1 = 4 " LC0#
2

k "

(23)

by merging all the constant terms into a constant factor k. This finally reveals the relation between the read frequency and the relative permittivity: ! ! ! k (24) "= 2 # After calibration with a liquid of known relative permittivity , the proportionality constant k can be ! determined. Experiment: The eigenfrequency of the pure solvent with known relative permittivity (heptane, heptane = 1.924 0.00140[T 200C] is therefore measured first (at least three measurements). With the obtained frequency , the constant k of the experimental setup is calculated. Then, the eigenfrequency of each solution is measured at three different concentrations (one time is enough) and the corresponding permittivities are calculated as described above. Then, is plotted against the weight fraction w2 (not the percentage) and the slope b is obtained:
$k' d& 2 ) d"(# radio ) %# ( b" = = dw 2 dw 2

(25)

2. The refractometer According to Maxwells theory, the relative permittivity () in the visible region of the electromagnetic spectrum can be easily determined using optical methods by measuring the refractive index at a given frequency. As shown in Fig. 3, in this part of the spectrum, the electronic polarization dominates and no contributions from orientation polarization or distortion polarization exist. The refractive index is measured with a refractometer as proposed by Abb. The technique is based on the phenomenon of total reflection. A light beam with an incidence angle in medium 1 hits a phase interface to an optically less dense medium 2. The angle of refraction in medium 2 is thus larger than . Using a relative angle of refraction
n= n1 sin " = >1 n 2 sin #

For normal refraction the relation


!
0 " n # sin $ = sin % " 1

always holds. An incident angle 0 < 900 must thus exist with
! sin " 0 = 1/n

If light hits a phase interface with an angle 0, the refracted light streaks the interface ( = 900). In case of angles > 0 the light beam is reflected at the interface. 0 is called the critical angle for total reflection. The Abb refractometer (Figure 5) contains two prisms made of vulnerable flint glass of high optical density (large n1), a prism for illumination and one for detection, a traversable telescope adjusted to infinity, and a lamp. The probe is in a layer with a thickness of 0.1 mm between the two prisms.

Figure 5: Schematic sketch of an Abb refractometer

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The incident light through the lighting prism is scattered on the mattfinished bottom side such that the probe is irradiated largely isotropically. Some light hits the detection prism under the critical angle of total reflection. For larger observation angles, the detection prism appears dark. The angle distribution of the leaving light is observed using a traversable telescope that is adjusted to infinity. In contrast to a microscope, not all the light that origins from one point of the examined object is mapped on one point of the eyes retina but all the light that enters the telescope with the same angle. Since white light is applied and since the refractive index varies with frequency (dispersion) no clear bright-dark edge appears in the visual field of the telescope, but a blurred coloured fringe. Using a compensator this fringe can be turned into a distinct bright-dark edge. This compensator consists of two parts, each one consisting of three Amici prisms that can be twisted against each other. This construction reveals a system of variable dispersion that can be used to calibrate the dispersion of lighting and detection prisms. To do so, the cross wire is adjusted on the bright-dark edge and the refractive index can directly be read on the shown scale. Experiment: First the refractive index of the pure solvent is measured as a reference. Then, the refractive index of each solution is measured for three different concentrations (the same solutions as for the dipole meter measurement are used). Since the refractive index changes only very slightly with concentration, each measurement has to be done three times and the average value is used. After each measurement the prism must be cleaned carefully. For the measurement, the prism must be wetted completely. The measurement has to be carried out fast enough such that no solvent can evaporate and falsify the result. With the obtained refractive indices n, the relative permittivity =n2 is the visible is calculated. Then is plotted against the weight factor w2 (not the percentage) and the slope bn is determined:

bn =

d"(# vis ) dn 2 = dw 2 dw 2

(26)

With bn and b all variables are known in order to calculate 0 according to the Guggenheim approximation.

3. Tasks 3.1. The dipole moments of chloro-cyclohexane, dichloromethane, trichloro-methane (chloroform) and monochloro-benzene are measured. 3.2. The calculated dipole moment of chloro-cyclohexane (1) is used to determine the ionic character of the C-Cl bond:

J=

1 d"e

(d = bond length C-Cl, e = elementary charge)

! The deviation from the vector sum due to alternating induction should be determined for 3.3. the dipole moments of dichloro-methane (2) and trichloro-methane (3).
=2 - 21 cos(2) 11

=3 - 21 cos(3) is the angle between the individual bond dipoles and the vector sum 3.4. Determine the reduction of the dipole moment (M) due to resonance in monochlorobenzene:
" = 1 # M

! 4.

Carrying out the experiment

At the beginning, dipole meter and thermostat are switched on. The apparatus has to reach a thermal stationary state before a measurement can be done. This takes about 15 min. The temperature of the thermostat may not change by more then 0.050 C during the experiment. Otherwise, the accuracy of refractive index and capacity are not accurate enough. Meanwhile three solutions of the substance received from the assistant are made in heptane, according to the following procedure: In a 50 ml graduate flask about 49 ml (the filled in amount has to be weighted exactly!) is filled in. Subsequently, using a syringe, as much substance is added such that a weight fraction of about 3% is obtained. Exactly 15 ml of this solution is put into a second flask (weight it exactly!). The remaining 35 ml are stored well closed and used later on for determining and n. The 15 ml are diluted with solvent to 50 ml and weighted again in order to exactly determine the weight fraction. It should approximately be 1%. The same procedure is applied to prepare a solution with a weight fraction of about 0.3%. It is very important that the solutions are prepared exactly according to this instruction! Use a small pipette in order to fill the cell with solution or solvent. Do it carefully and make sure, that the pipette doesnt break. Any air that could be captured in the cell would disturb the measurement. After filling in solvent or solution, always wait about 5 min. until the solvent is in thermal equilibrium with the apparatus. Then the eigenfrequency is measured using the frequency counter. As a first measurement, the relative permittivity of the pure solvent is determined. For this purpose the measuring cell is filled with solvent (heptane). The frequency is determined at least three times and the results are averaged. From the measurement, constant k in Eqn 24 is determined. In all subsequent measurements of solutions, it has to be ensured that the cell is clean and dry before a solution is filled in such that the concentrations are not changed. The cell has to be blown out with the dryer first hot, then cold, until no solvent can be smelled. After one measurement, the cell is cleaned with solvent and the solvent is measured again. Finally, a plot is generated according to Eqn. 25. In parallel vis is determined by measuring the refractive indices of solvent and solutions. Using a pipette solvent or solution is put on the detection prism. Then, the lighting prism is put on using the bayonet nut connector. The prisms are cleaned using Linsoft tissues and acetone or ethanol. They may not be scratched! A plot is accomplished according to Eqn. 26. The density 1 of the solvent is indicated in the lab and the molar weight of the dissolved substance M2 is known. All variables in order to calculate 0 according to the Guggenheim equation are now known. 12

5.

Practical advices 5.1. Preparing the solutions 5.1.1. The indicated concentrations have not to be kept exactly. The concentrations have, however, to be known exactly 5.1.2. Check carefully that pipettes, flasks, etc are clean 5.1.3. Use different pipettes for different substances 5.1.4. Always close the flasks to avoid change of concentration due to vaporization 5.1.5. Keep the solutions after the measurements in case you have to repeat some of the measurements. 5.2. General remarks 5.2.1. All constants are in the SI system: e = 1.602177 10-19 C 0 = 8.85419 10-12 J-1C2m-1 5.2.2. Begin with low concentrations and move consequently to higher ones. 5.2.3. When the concentration is changed, the cell has to be rinsed twice with pure solvent, be dried with the dryer until no solvent can be noticed. 5.2.4. Check carefully the temperature during the whole experiment. 5.2.5. Wait ten min. after a solution has been filled in such that thermal equilibrium is reached. 5.2.6. Repeat every measurement three times and average the results. 5.2.7. 1 = heptane = 1.924 0.00140[T 200C] 1 = heptane = 0.681 g/cm3 M1=Mheptane= 100g/mol d = bond length C-Cl = 1.77 A 2 = 7200 3 = 55053
0

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Literature: 1. G. Wedler, Lehrbuch der Physikalischen Chemie, 2. Auflage, VCH Verlagsgesellschaft, Weinheim, 1985 2. P.W. Atkins, Physical Chemistry, 5. Edition, Oxford University Press, 1994 3. C.F.J. Bttcher, Theory of Electric Polarization, 2. Edition, Elsevier, New York, 1973 and 1978. 4. H.B. Thompson, The Determination of Dipole Moments in Solution, J. Chem. Educ. 1966, Vol.43, pp. 66 - 73

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