J.

Atoms and Molecules / 3(1); 2013 / 469473 Research Article

Shere IG

Journal of Atoms and Molecules

An International Online Journal
ISSN 2277 1247

MOLECULAR INTERACTIONS OF BUTANENITRILE WITH CHLOROBENZENE AT 100C USING MICROWAVES

*

I. G. Shere* Department of Electronics, Shri. Havagiswami Mahavidyalaya, Udgir-413517 Maharashtra Revised on: 24-02-2013 Accepted on: 28022013

Received on: 12-02-2013 ABSTRACT:

The dielectric spectra of Butanenitrile(BN) with Chlorobenzene(CBZ) mixture has been studied at temperature 100C 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. The values of static dielectric constant are fitted in Bruggeman Model. In the mixtures the values of geff are less than one and it shows that there is antiparallel alignment of dipoles. The more deviation from Bruggeman parameter shows stronger interaction between the molecules in the mixture. KEY WORDS: Nitrile group, Chloro group, Dielectric parameters, Kirkwood Parameters, Bruggeman 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 Butanenitrile and Chlorobenzene. 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 molecular interaction strength and also the correlation between butanenitrile and chlorobenzene mixture using TDR at 100C temperature.

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

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J. Atoms and Molecules / 3(1); 2013 / 469473 MATERIALS & APPARATUS: A spectrograde Butanenitrile(BN) (Fluka cheme Gmbh-9471 Buchs, Steinheim, Swizerland) and AR grade Chlorobenzene(CBZ) ( E-Merck) were used without further purification The density and molecular weight of the liquids are as follows: Butanenitrile -density: 0.8329 gm cm-3; mol.wt.-67.09. Chlorobenzene-density: 1.105 gmcm-3; mol.wt.-112.56 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 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). All rights reserved 2011

Shere IG 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-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 Kirkwood correlation factor gf et al Frolhich (1949) is 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

(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 BN and CBZ in gas phase are taken as 3.91D and 1.69 D et al Weast (1983) respectively. For the mixture of two polar liquids 1, 2 Eq. (3) is modified by ref. et al 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 2 eff (0m m )(20m +m ) 4N 12 1 1 + 2 2 g = 9kT M1 M2 0m (m +2)2 (4)

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J. Atoms and Molecules / 3(1); 2013 / 469473 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 ( )(2 + ) g 4N 12 1g1 2 g f = 0m m 0m 2 m 1+ 2 2 2 9kT M1 M2 0m(m +2) (5)

Shere IG Number in bracket represent error in the corresponding value, e.g. means 10.76(3) means10.760.03 In equation (4), 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 angular correlation between the molecules of the system. Temperature dependent geff and gf for the system are shown in Figure (1).
0.65
(a)

where geff is the effective Kirkwood correlation factor for a binary mixture, with 1 and 2 as volume fractions of liquids 1 and 2 respectively. The static dielectric constant (0) and relaxation time () obtained by fitting experimental data with the Debye equation for 100C temperature is listed in Table 1. The values of static dielectric constant (0) increases and relaxation time () values decreases with the increase of concentration of BN in CBZ. Table1: Static dielectric constant (0) and relaxation time () for 100C temperature
Volume % of BN 0 10 20 30 40 50 60 70 80 90 100

0.6

0.55 g
eff

0.5

0.45 0 0.25 0.5 0.75 1 Volume fraction of BN in CB

0
6.78(0) 9.13(0) 11.08(0) 13.40(0) 15.17(0) 17.44(0) 19.24(0) 21.32(1) 24.30(1) 26.39(1) 29.32(1)

(ps)
11.94(7) 12.53(3) 12.96(2) 12.53(1) 12.03(2) 11.71(1) 11.31(2) 10.76(3) 10.27(3) 9.65(4) 9.69(3)

1.01
(b)

gf

0.99 0.98 0.97 0.96 0 0.25 0.5 0.75 1 Volume fraction of BN in CB

Figure 1 (a) Kirkwood effective correlation factor geff and (b) Kirkwood correlation factor gf, versus volume fraction (2) of BN in CBZ.

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J. Atoms and Molecules / 3(1); 2013 / 469473 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 more. The more deviation in gf values shows that stronger 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 The modified Bruggeman equation et al Kumbharkhane (1993) is another parameter, which may be used an indicator of liquid 1 and 2 interaction. The Bruggeman factor fB is given by,
0 m 02 f B = 01 02 01 0 m
1/ 3

Shere IG
1
Theo. Expt.

0.75

Ideal

0.5 fB 0.25

0 0 0.2 0.4 0.6 0.8 Vol. fraction of BN in CB 1

Figure 2 The Bruggeman plot for BN-CBZ mixture. CONCLUSION:

= (1 2 )

(6)

According to equation (6), a linear relationship is expected which will give a straight line when plotted fB against 2. However, here the experimental values of fB were found to deviate from the linear relationship. The Bruggeman dielectric factor fB versus volume fraction 2 of BN at 10C is shown in Figure 2. To fit the experimental data, Eq.(6) has been modified et al Puranik (1994) fB=1-[a-(a-1)2]2 (7)

The Kirkwood correlation factors have been reported by the use of the dielectric parameters for BN-CBZ mixtures for 100C temperature and different 11-concentrations. The correlation of the chlorine group CBZ with the CN bonded liquid BN is discussed. It is found that the antiparallel alignment of the dipoles of the molecules of the mixture. It also shows that stronger interaction between the BN and CBZ molecules. The Bruggeman parameter also confirms that the stronger interaction between the constituent molecules of the mixture.

ACKNOWLEDGEMENT:
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.

Where 'a' is numerical fitting parameter. The parameters a has been determined by the least squares fit method and it is found to be 0.761. The value of a = 1 corresponds to the ideal Bruggeman mixture formula. The deviation from 1 relates to interaction between corresponding liquids 1 and 2. The large deviation of a suggest that stronger interaction between BN and CBZ.

REFERENCES:
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J. Atoms and Molecules / 3(1); 2013 / 469473 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. C. E. Shannon, Proc. IRE, 37 (1949) 10. H. A. Samulan, Proc. IRE, 39 (1951) 175. P. Debye, Polar molecules, Chemical Catalog, New York (1929). [11] [8]

Shere IG P. R. Bevington, Data reduction and error analysis for the physical sciences, Mc-Graw Hill, New York, (1969). H. Frolhich, Theory of dielectrics, Oxford University Press, London, (1949). R. C. Weast, Handbook of Chemistry and Physics, 64th ed. CRC Press Boca Raton, Florida, (1983-84). A. C. Kumbharkhane, S. M. Puranik and S. C. Mehrotra, J. Sol. Chem., 22(1993) 219. S. M. Puranik, A. C. Kumbharkhane and S. C. Mehrotra, J. Mol. Liq., 59(1994)173.

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