J.

Atoms and Molecules / 3(2); 2013 / 505508 Research Article

Shere IG

Journal of Atoms and Molecules

An International Online Journal
ISSN 2277 1247

DIELLECTRIC RELAXATION STUDY OF PENTANENITRILE WITH DICHLOROETHANE AT 350C USING TDR I. G. Shere*
*

Department of Electronics, Shri. Havagiswami Mahavidyalaya, Udgir-413517 Maharashtra, India. Revised on: 11-04-2013 Accepted on: 17042013

Received on: 22-03-2013 ABSTRACT:

The dielectric spectra of Pentanenitrile(PN) with 1, 2 Dichloroethane(DCE) mixture has been studied at temperature 350C in the frequency range of 10 MHz to 20 GHz using time domain reflectometry (TDR) for 11 different concentrations of the system. The dielectric parameters such as static dielectric constant (0) and relaxation time () have been obtained by Fourier transform and the least squares fit method. The dielectric parameters such as static permittivity and relaxation time for the mixture have been reported. The excess dielectric constant and excess inverse relaxation time have also studied. The investigation shows that the effective dipoles increases and the dipoles rotate slowly due to the hindering field between the constituent molecules of the PN and DCE mixture. KEY WORDS: Dielectric permittivity, Relaxation time, Nitrile group, Chloro group, Excess dielectric parameters.

INTRODUCTION: The dielectric relaxation study of molecular mixture at microwave frequencies gives information about formation of monomers and multimers as well as interaction between the molecules of the mixture et al Helambe (2000), Pawar (2002). The molecules taken for the study are Pentanenitrile and 1, 2 Dichloroethane. One is of nitrile group and other with chlorine group. It is interesting to see the effect of nitrile group with chlorinegroup. The objective of the present paper is to report the dynamics of the molecule between pentanenitrile and dichloroethane mixture using TDR at 350C temperature.

* Corresponding author I. G. Shere, Email: shereishwar@yahoo.in Tel: +91 -7709672319

All rights reserved 2011

www.jamonline.in 505

J. Atoms and Molecules / 3(2); 2013 / 505508 MATERIALS AND APPARATUS: A spectrograde Pentanenitrile (PN) (Fluka cheme Gmbh-9471 Buchs, Steinheim, Switzerland) and AR grade 1, 2 Dichloroethane (DCE) (E-Merck) were used without further purification. The density and molecular weight of the liquids are as follows: Pentanenitrile -density: mol.wt.-81.12. 0.795 gm cm-3;

Shere IG The experimental values of * are fitted with the Debye equation et al (1929) *() = +

o 1 + j

(2)

1, 2 Dichloroethane -density: 1.256gmcm-3; mol.wt.-98.96. The complex permittivity spectra were studied using the time domain reflectometry et al Cole (1989), Puranic (1991) method. The Hewlett Packard HP 54750 sampling oscilloscope with HP 54754A TDR plug in module has been used. The change in the pulse after reflection from the sample placed in the cell was monitored by the sampling oscilloscope. The reflected pulse without sample Rl(t) and with sample Rx(t) were digitized in 1024 points in the memory of the oscilloscope and transferred to a PC through 1.44 MB floppy diskette drive. DATA ANALYSIS The time dependent data were processed to obtain complex reflection coefficient spectra *() over the frequency range from 10 MHz to 20 GHz using Fourier transformation et al Shannon(1949), Shamulan(1951) as *()=(c/jd)[p()/q()] (1) Where p() and q() are Fourier transforms and [R1(t)+Rx(t)] of [R1(t)-Rx(t)]) respectively, c is the velocity of light, is angular frequency, d is the effective pin length and j= 1 . The complex permittivity spectra *() were obtained from reflection coefficient spectra *() by applying bilinear calibration method et al Cole (1989).

With 0, and as fitting parameters. A nonlinear least-square fit method et al. Bevington (1969) was used to determine the values of dielectric parameters. In Eq. (2), 0 is the static dielectric constant, is the limiting high-frequency dielectric constant and is the relaxation time.

RESULTS AND DISCUSSION

The static dielectric constant (0) and relaxation time () obtained by fitting experimental data with the Debye equation are listed in Table 1. The values of static dielectric constant (0) increases and relaxation time () values shows no trend with the increase of concentration of PN into DCE.

Table1: Static dielectric constant (0) and relaxation time () for 350C temperature
Volume percentage 0 of PN in DCE 0 10 20 30 40 50 60 70 80 90 100 10.1 12.29 13.86 14.71 15.32 15.88 16.76 17.24 17.62 18.2 19.38 (ps) 10.12 12.12 12.33 13.35 12.47 12.28 13.06 12.75 11.61 12.28 11.5

All rights reserved 2011

www.jamonline.in 506

J. Atoms and Molecules / 3(2); 2013 / 505508 Figure 1(a) Shows behavior of excess permittivity and (b) the excess inverse relaxation time for the system as a function of volume concentration of PN in DCE at 350C temperature The information related to liquids 1 and 2 interaction may be obtained by excess properties et al Tabellout (1990) related to the permittivity and relaxation times in the mixture. The excess permittivity E is defined as
E=(0 )m-[(0 )1 x1+ (0 )2 x2] (3)

Shere IG Similarly, the excess inverse relaxation time is defined as (1/)E = (1/)m-[(1/)1 x1+(1/)2 x2 ] (4) where (1/)E is excess inverse relaxation time which represents the average broadening of dielectric spectra. The inverse relaxation time analogy is taken from spectral line broadening (which is inverse of the relaxation time) in the resonant spectroscopy et al Mehrotra (1977) The experimental values of both the excess parameters were fitted to the RedlichKister equation et al Aralaguppi (1991) and AlAzzawl (1990) AE = (x1 x2) Bn ( x1 x 2 )n
n

Where x- mole fraction and suffices m, 1, 2 represents mixture, liquid 1 (PN) and liquid 2 (DCE) respectively. The excess permittivity may provide qualitative information about multimers formation in the mixture.
2.5 (a) 2 1.5
E

Where A is either E or (1/) E. By using these Bn values, AE values were calculated. The excess permittivity (E) increases sharply towards the peak value then decreases slowly and goes also in the negative region up to pure PN. In the PN-DCE system excess permittivity (E) curve, the peak value is noted at 0.2486 mole fraction of PN in DCE. Then it shows that there is a linear decrease. The value goes in negative only for concentration 0.8742.The E values are positive in DCE rich region. Hence there is formation of monomeric or polymeric structures. The total effective dipole increases. There is a parallel alignment of dipoles in DCE rich region. The values of excess permittivity are negatives in PN rich region. It indicates that there is decrease in dipole of the mixture. Hence there is anti parallel alignment of dipoles in PN rich region. The excess inverse relaxation time values are negatives for all concentrations. It also shows that there is sudden increase in (1/) E from 0 to 0.1618 concentration of PN. The negative values of inverse relaxation time indicate that; an opposing field in the dipoles and the www.jamonline.in 507

0.5 0 0 -0.5 0.2 0.4 x2 0.6 0.8 1

Figure 1. (a)The excess permittivity (E) versus volume fraction of PN into DCE.

0 0

0.25

x2 0.5

0.75

-5 (1/)
E

-10

-15 (b) -20

(b) The excess inverse relaxation time (1/) E versus volume fraction of PN into DCE. All rights reserved 2011

J. Atoms and Molecules / 3(2); 2013 / 505508 slower effective dipole rotation of the molecules in the system. CONCLUSION The dielectric parameters such as static dielectric permittivity and relaxation time have been reported for PN-DCE mixtures at 350C temperature for 11 different concentrations. The excess dielectric parameters are also obtained. The values of excess permittivity are positives except 0.8742 concentrations and it indicates that; the effective dipoles form monomers and also increases. The excess inverse relaxation time values are negative for all concentrations and it shows that; the dipoles in the mixture form opposing field and dipole rotates slowly. ACKNOWLEDGEMENTS The author is thankful to V.P Pawar (Udgir) and S.C. Mehrotra, Head, Dept. of Computer Science, Dr. B.A.M.University, Aurangabad for valuable guidance. REFERENCES 1. S. N. Helambe, A. S. Chaudhary and S. C. Mehrotra, J. Mol. Liq.,84 (2000) 235 2. V.P. Pawar, S. C. Mehrotra, J Mol.Liq., 95 (2002)63-74.

Shere IG 3. R. H. Cole, J. G. Berbarian, S. Mashimo, G. Chryssikos, A. Burns and E. Tombari, J. Appl.Phys.,66 (1989) 793. 4. S. M. Puranik, A. C. Kumbharkhane and S. C. Mehrotra, J. Chem. Soc. Faraday Trans., 87 (1991) 1569. 5. C. E. Shannon, Proc. IRE, 37 (1949) 10. 6. H. A. Samulan, Proc. IRE, 39 (1951) 175. 7. P. Debye, Polar molecules, Chemical Catalog, New York (1929). 8. P. R. Bevington, Data reduction and error analysis for the physical sciences, McGraw Hill, New York, (1969). 9. M. Tabellout, P. Lanceleur, J.R. Emery, D. Hayward and R.A. Pethrick, J.Chem.Soc.FaradayTrans. , 86(1990)1493. 10. S.C. Mehrotra and JE Boggs, J. Chem. Phys., 66(1977) 5306. 11. M.I. Aralaguppi, T.M. Aminabhavi, R.H. Balundgi and S.S. Joshi, J. Phy. Chem., 95(1991)5299. 12. S.F. Al-Azzawl, A.M. Awwad, A.M. AlDujaili and M.K. Al-Noori, J. Chem.Engg.Data,35(1990)463.

All rights reserved 2011

www.jamonline.in 508

J. Atoms and Molecules / 3(2); 2013 / 505508

Shere IG

All rights reserved 2011

www.jamonline.in 509