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Shere IG

An International Online Journal

ISSN 2277 1247

STUDY THE MOLECULAR CORRELATION OF PENTENENITRILE WITH 1,2 DICHLOROETHANE AT 450C TEMPERATURE I. G. Shere*

*

Department of Electronics, Shri. Havagiswami Mahavidyalaya, Udgir-413517 Maharashtra, India. Revised on: 14-10-2012 Accepted on: 20102012

The dielectric relaxation study of 2-pentenenitrile(PN) with 1, 2 Dichloroethane(DCE) mixture has been carried out at temperature 450C 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. Kirkwood correlation factor (gf) and effective Kirkwood correlation factor (geff ) of the mixtures have been determined. In the mixtures the values of geff are less than one and it shows that there is antiparallel alignment of dipoles Key Words: Dielectric parameters, Kirkwood Parameters, Time Domain Reflectometer, nitrile, Chlorine group. Introduction: The dielectric relaxation study of solutesolvent mixture at microwave frequencies gives * Corresponding author I. G. Shere, Email: shereishwar@yahoo.in Tel: +91 7709672319 information and about formation as well of as

monomers

multimers

interaction between the molecules of the mixture et al Helambe(2000), Pawar(2002). Pentenenitrile (PN) is non-associative liquids and 1, 2 Dichloroethane (DCE) is associative liquid. One is of nitrile group and other with chlorine group. It is interesting to see the effect of nitrile group with chlorine-group. The objective of the present paper is to report

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J. Atoms and Molecules / 2(5); 2012 / 351355 the detailed study of molecular correlation between pentenenitrile and 1,2 Dichloroethane mixture using TDR at 450C temperature. Materials and methods: A spectrograde 2-pentenenitrile(Fluka cheme Gmbh-9471 Buchs, Steinheim, Swizerland) and AR grade 1,2 Dichloroethane ( E-Merck) were used without further purification The density and molecular weight of the liquids are as follows: 2-Pentenenitrile-density: mol.wt.-81.12. 1,2Dichloroethane-density: 1.256 gm cm-3; mol.wt.-98.96 The complex permittivity spectra were 0.795 gm cm-3; Shannon(1949),

*()=(c/jd)[p()/q()]

Where p() and q() are Fourier transforms of [R1(t)-Rx(t)]) and [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). The experimental values of * are fitted with the Debye equation et al (1929) *() = +

o 1 + j

(2)

with 0, , and as fitting parameters. A nonlinear least-squares 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. The Kirkwood correlation factor gf et al Frolhich(1949) is also a parameter for getting information regarding orientation of electric dipoles in polar liquids. The gf for pure liquid may be obtained by the expression ( )(2 0 + ) 4 N 2 gf = 0 9k T M 0 ( + 2) 2

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 All rights reserved 2011

(3)

where is dipole moment in gas phase, is density at temperature T, M is molecular weight, k is Boltzman constant, N is Avogadros number. The dipole moments for

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J. Atoms and Molecules / 2(5); 2012 / 351355 ACN and DCE in gas phase are taken as 3.95D and 2.06 D et al Weast(1983) respectively. For the mixture of two polar liquids 1, 2 Eq. (3) is modified by ref. et al

Shere IG experimental data with the Debye equation for 450C temperature are listed in Table 1. The values of static dielectric constant (0) increases with the increase of concentration of PN in DCE and relaxation time () values have no trend. Table1: Static dielectric constant (0) and relaxation time () for 450C temperature.

Kumbharkhane(1993) with the following assumptions: 1. Assume that g for the binary mixture is expressed by an effective averaged correlation factor geff such that the Kirkwood equation for the mixture can be expressed by

2 4N 1 1 22 eff (0mm)(20m+m) 2 (4) M 1+ M 2 g = ( +2)2 9kT 1 2 0m m

Volume % of PN 0 10 20 30 40 50 60 70 80

(ps)

9.81(0) 10.33(0) 10.57(0) 10.66(0) 10.8(0) 10.88(0) 10.99(0) 11.07(0) 11.15(0) 11.2(0) 11.33(0)

9.9(0) 10.93(2) 11.04(0) 11.32(3) 11.12(0) 11.1(2) 11.28(4) 11.24(3) 10.98(1) 11.16(3) 10.94(0)

with 1 and 2 as volume fractions of liquids 1 and 2 respectively. 2. Assume that the correlation factors for molecules 1 and 2 in the mixture contribute to the effective g proportionality to their pureliquid values g1, g2. Under this assumption the Kirkwood equation for the mixture can be written

2 4N 1 1g1 22g2 (0mm)(20m+m) 2 (5) M 1+ M 2 gf = ( +2)2 9kT 1 2 0m m

where

eff

is

the

effective

Kirkwood 90 100

correlation factor for a binary mixture, with 1 and 2 as volume fractions of liquids 1 and 2 respectively. Results and Discussion: The static dielectric constant (0) and

Number in bracket represent error in the corresponding value, e.g. means 11.16(3) means11.160.03

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In equation (5), the values of geff will change from g1 to g2 as concentration of molecule 2 will decrease from 100% to 0%. The Kirkwood correlation factor(gf) which gives

Shere IG

angular correlation between the molecules of the system. Temperature dependent geff and gf for the system is shown in Figure (1).

eff

0.4 0.3 0.2 0.1 0 0.2 0.4 0.6 0.8 1 Volume fraction of PN in DCE

Figure 1. (a) Kirkwood effective correlation factor geff and (b) Kirkwood correlation factor gf, versus volume fraction (2) of PN in DCE. The values of geff are less than one and it indicates that there is antiparallel alignment of dipoles. The deviation of gf values from unity is little. The Small deviation in gf values shows that weaker interaction between the constituent molecules in the system. The values of geff and gf are calculated from equation (4) and (5) for the mixtures of the system Conclusion: The Kirkwood correlation factor has been reported for ACN-DCE mixtures for 450C temperature and different 11-concentrations. The correlation of the chlorine group DCE with the CN bonded liquid ACN is discussed. It shows that stronger interaction between the PN and DCE molecules. One 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 observes significant deviation from the

Mol.Liq.,95(2002)63-74. 3. R. H. Cole, J. G. Berbarian, S. Mashimo, G. Chryssikos, A. Burns and E. Tombari, J. Appl.Phys.,66 (1989) 793.

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J. Atoms and Molecules / 2(5); 2012 / 351355 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. H. Frolhich, Theory of

Shere IG dielectrics,

Oxford University Press, London, (1949). 10. R. C. Weast, Handbook of Chemistry and Physics, 64th ed. CRC Press Boca Raton, Florida, (1983-84). 11. A.C. Kumbharkhane, S. M. Puranik and S. C. Mehrotra, J. Sol. Chem., 22(1993) 219.

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