International Journal of Research in Pharmaceutical and Biomedical Sciences

ISSN: 2229-3701

_____________________________________________Research Article

Studies of Molecular Interaction of Phenol With Xylenes Through Excess Parameters

M. Meenachi and P. Krishnamurthi Department of Physics, Jayam College of Engineering and Technology, Dharmapuri, Tamil Nadu, India.
ABSTRACT Refractive indices and densities of binary liquid mixture of phenol with o-xylene, p-xylene, m-xylene were measured over the entire composition range at 303K. These measured data were utilized to evaluate the molar volume (Vf), excess molar volume ( Vf E), excess refractive index (nE), molar refraction (Rm), Polarisability (), atomic polarization(Pa) and solvated radii (r) of the mixed solvents. which indicates the existence of weak molecular interaction like solute- solvent interaction. Key Words: Atomic polarization, density, excess parameter, molar volume, refractive index, polarizability. 1. INTRODUCTION The study of molecular interaction plays an important role in the development of chemistry, medical and biological process . The physical property data on mixed solvent are important for theoretical and applied areas of research and are frequently used in many chemical and industrial process1. Refractive index and density measurements of binary liquids are essential for determination of molecular interaction for non ideal mixtures behavior where direct experimental measurements are performed over the entire composition range2.The excess properties of mixtures provide the information about the molecular interaction between the various components3. The present investigation deals with the measurements of refractive index and density of the phenol + o-xylene, phenol+p-xylene, phenol +xylene. From the Experimental data evaluate the molar volume ( Vf), excess molar volume(VfE), molar refraction(Rm),polarisability(), Atomic polarization(Pa) and solvated radii (r) of these mixtures over the entire mole fraction ranges have been calculated. 2. EXPERIMENTAL The phenols, o-xylene , p-xylene, m-xylene are used in this present investigation purified according to the methods by Riddick et al4. The refractive indices of the mixtures were measured using an Abbes refractometer with an accuracy of 0.0001. The densities have been measured with 25ml specific gravity bottle at 303K. 3. THEORY AND CALCULATION The excess refractive index (nE) were determined using the relation

n E =n12 -(1n1 +2 n 2 )

(1)

1 And 2 are mole fraction of the component, n1 ,n2 and n12 are refractive indices of pure component and binary mixtures respectively.

x1 1 ) m1 The molar volume 1 x x ( 1 1)( 2 2) m1 m2 (

n12 2 1 V12 n12 2 2

and

x 2 2 ) m1 2 x x ( 1 1)( 2 2 ) m1 m2 (

.(2)

Where 1, 2, m1, m2, x1 , and x2 are the densities, molecular weights and mole fractions of the components. The molar refraction was also calculated using the equation5

(3)

Vol. 3 (4) Oct Dec 2012

www.ijrpbsonline.com

1719

International Journal of Research in Pharmaceutical and Biomedical Sciences

ISSN: 2229-3701

Where

V12

m1x1 m 2 x 2 12

The molar volume can be calculated from the equation M /, where M and are the molecular weight and density of binary mixtures and the effective molecular weight Meff = 1 1 M1+ 2 M2 --- (4) The atomic polarization can be calculated from the equation6 PA= 1.05n2 (5) The dipole moment induced by the electric field can be calculated from the optical refractive index of a material. The refractive index is related to the polarizability of molecules by Lorentz- Lorentz formula7

n12 2 1 4 n n12 2 2 3

...(6)

Where n= Na / m is N the Avogadro number and is the density m is the effective molecular weight . The solvated radii (ra) have been calculated by assuming the spherical shape of solvated molecules, given by the expression8

4 3 r 3

(7)

RESULTS AND DISCUSSION The experimental values of refractive index( n12) and density (12) and calculated value of molar refraction (R), molar volume(V), atomic polarization(Pa), polarizability( ) and solvated radii( r) at 303K are presented in table 1 to 3. The plots of the excess refractive indices (nE), excess molar refraction( R) and excess molar volume (V), Vs volume fraction are shown in fig. 1 -3. The variation of excess refractive index of the mixtures with molar volume of phenol with o-xylene, p-xylene, m-xylene at 303 K appears in Fig. 1. The deviations in excess refractive index as shown in fig. 1 are negative for all the three binary systems (phenol + o-xylene/m-xylene/pxylene) under study over the whole composition range.

Table 1:The mole fractions of Phenol with o-xylene, excess refractive indices nE,10-3 ),molar volume(V 103 ),molar refraction (R 103Litre),atomicpolarization(Pa),polarizability(,10-26),Solvated radii(r,10-10)

Vol. 3 (4) Oct Dec 2012

www.ijrpbsonline.com

1720

International Journal of Research in Pharmaceutical and Biomedical Sciences

ISSN: 2229-3701

Table 2:The mole fractions of Phenol with o-xylene , excess refractive indices nE,10-3),molar volume(V 103 ),molar refraction (R 103Litre),atomicpolarization(Pa),polarizability(,10-26),Solvated radii(r,10-10)
p-xylene

0.0762 0.1159 0.1567 0.1985 0.2415 0.3313 0.4263 0.5271 0.6342 0.7483 0.8699

n12 1.5034 1.5048 1.5063 1.5078 1.5093 1.5122 1.5152 1.5182 1.5211 1.5241 1.527

12 0.882 0.8925 0.903 0.9135 0.924 0.945 0.966 0.987 1.008 1.029 1.05

R 35.4 34.82 34.35 33.88 33.41 32.49 31.59 30.69 29.8 28.92 28.03

V 119.67 117.45 115.55 113.69 111.85 108.24 104.71 101.25 97.85 94.5 91.18

Pa 2.37 2.38 2.38 2.39 2.39 2.4 2.41 2.42 2.43 2.44 2.45

1.4038 1.381 1.3622 1.3435 1.325 1.2884 1.2526 1.2172 1.1818 1.1468 1.1116

r 6.56 6.52 6.48 6.45 6.41 6.34 6.27 6.2 6.13 6.06 5.99

Table 2:The mole fractions of Phenol with o-xylene , excess refractive indices nE,10-3),molar volume(V 103 ),molar refraction (R 103Litre),atomicpolarization(Pa),polarizability(,10-26),Solvated radii(r,10-10)
m-xylene

0.0762 0.1159 0.1567 0.1985 0.2415 0.3313 0.4263 0.5271 0.6342 0.7483 0.8699

n12 1.504 1.5057 1.5074 1.5091 1.5107 1.5138 1.5169 1.5198 1.5225 1.5251 1.5276

12 0.8852 0.8971 0.9088 0.9203 0.9316 0.9536 0.975 0.9956 1.0156 1.0348 1.0532

R 35.29 34.69 34.19 33.7 33.21 32.27 31.37 30.5 29.64 28.8 27.97

V 119.16 116.83 114.8 112.83 110.92 107.24 103.72 100.35 97.1 93.95 90.89

Pa 2.38 2.38 2.39 2.39 2.4 2.41 2.42 2.43 2.43 2.44 2.45

1.3993 1.3759 1.3558 1.3363 1.3171 1.2799 1.2442 1.2095 1.1753 1.142 1.1092

r 6.55 6.5 6.47 6.43 6.39 6.32 6.25 6.18 6.12 6.05 5.98

. Fig. 1: plots of excess refractive index (n ) vs volume fraction ( 2 ) The negative nE values are generally observed for the systems where dispersion or weak dipole-dipole forces are primarily responsible for the interaction between the component molecules. In the systems under study, phenol molecules are highly polar and aromatic hydrocarbon molecules are non-polar having -electrons on the ring.
E

Vol. 3 (4) Oct Dec 2012

www.ijrpbsonline.com

1721

International Journal of Research in Pharmaceutical and Biomedical Sciences

ISSN: 2229-3701

On mixing, a phenol molecule would induce a small dipole moment in the aromatic hydrocarbon molecule, which might lead to weak dipole-induced dipole interaction between the component molecules, in addition to donor- acceptor interaction between -electrons of benzene ring of the hydrocarbons and highly polar OH group of phenol, resulting in negative values. Negative deviation in nE values may also be observed due to the position of CH3 group. Molecular size of the component molecules, as in the present mixtures. The magnitude of negative nE values (Fig. 1) follows the sequence: m-xylene> p-xylene > o-xylene9-13.

Fig. 2: plots of excess molar refraction (RE ) vs volume fraction ( 2 ) The deviations in molar refraction (R) are shown in Fig. 2, all the three binary mixtures are negative for phenol +o-xylene/p-xylene/m-xylene. The magnitude of negative RE values follows the order: m-xylene <o-xylene < pxylene. In general, the negative values R suggest weak interactions between the component molecules in the mixture. Thus, the observed trends in RE values with composition support the trends shown by nE for the mixtures under study. This is also the sequence in the difference in molar volumes of phenol and aromatic hydrocarbons in the present study. For all the mixtures, the values become more negative to xylenes as shown in fig.3. Also for xylenes, the extent of negative deviation in VE suggests that the position of methyl groups on the aromatic ring influences the VE values in these mixtures. We thus conclude that the magnitude of VE, for the present systems, depends on the position of -CH3 groups in the ring of the aromatic hydrocarbons.

Fig. 3: plots of excess molar volume (VE ) vs. volume fraction ( 2 ) CONCLUSION From the n and and related excess parameters of phenol with o-xylene, p-xylene, m-xylene for different concentrations at 303K have been computed. It has been found the existence of weak dipole induced dipole interaction in the order of m-xylene > p-xylene > o-xylene. REFERENCES 1. Martindale J and Reynolds FF 1982 The extra pharmacopoeia28th edn (London: Pharmaceutical Press)

Vol. 3 (4) Oct Dec 2012

www.ijrpbsonline.com

1722

International Journal of Research in Pharmaceutical and Biomedical Sciences

ISSN: 2229-3701

2.

B S Narwade, P G Gawali, Rekha pande and Kalamse GM. Dielectric studies of binary mixtures of npropyl alcohol and ethylenediamine. J Chem Sci. 2005; 117(6): 673-676. 3. Sangit Sharma Pragnesh B Patel, Rignesh S Patel and Vora JJ.Density and Comparative Refractive index Study on mixing properties of Eucalyptol with Hydrocarbons at 303.15,308.15K. E-Journal of chemistry. 2007;4(3):343-349. 4. Riddick JA, Bunger WB and Sukano TK. Organic solvents: Physical properties and methods of purification, 2, Fourth Edition, McGraw-Hill, New York, 1986. 5. Moody GJ and Thomas JDR. Dipole moments in Inorganic Chemistry, Edward Arnold :London 1971 6. Mongnaschi ER and Laboranti LMJ. Chem Soc Faraday Trans.1996;92(18):3367. 7. Hasted JB.Aqueous Dielectrics: Chapman and Hall: London, 1973 8. Kim JIZ. Phys chem. NeueFolge.1978;113:129 9. Reid RC, Prausnitz JM and Sherwood TK. The properties of gases and Liquids , Third edition, McGraw-Hill, New York,1977. 10. Roberts CW and Melvin JA. CRC Hand book of Data on organic Compounds, CRC Press, Boca Raton, Florida, 1985. 11. Farid I and El-Dossoki. Refractive index and density measurements for selected Binary protic- Protic, Aprotic-Aprotic and Aprotic-Aprotic systems at temperatures from 298.15K to 308.15K. Journal of the Chinese Chemical Society. 2007;54:1129-1137.

Vol. 3 (4) Oct Dec 2012

www.ijrpbsonline.com

1723