Elsevier

Fluid Phase Equilibria

Volume 387, 15 February 2015, Pages 121-134
Fluid Phase Equilibria

Refractive properties, speed of sound and FT-IR study of binary mixtures of N-formylmorpholine with some halobenzenes at 303.15, 308.15 and 313.15 K

https://doi.org/10.1016/j.fluid.2014.12.012Get rights and content

Abstract

Refractive indexes (ηD), speed of sound (u) have been measured for binary mixtures of N-formylmorpholine + fluorobenzene, + chlorobenzene, + bromobenzene at 303.15, 308.15 and 313.15 K and at atmospheric pressure over whole composition range. Deviation in refractive index (ΔηD), molar refraction (Rm) and deviation in molar refraction (ΔRm) have been calculated using measured values of refractive indexes. Deviation in speed of sound (Δu), deviation in isentropic compressibilityks) and deviation in acoustic impedancez) have been calculated from measured values of speed of sound. Theoretical refractive index values are calculated using nine relations namely Arago–Biot (A–B), Dale–Glastone (D–G), Lorentz–Lorentz (L–L), Weiner (WR), Heller (Hr), Newton (Nw), Eyring–John (E–J) Eykman (Eyk), Oster (Os) and their average deviation with experimental measured values have been calculated. Theoretical speed of sound is also calculated by using relations like Nomoto’s relation, Ideal mixture relation, Junjie’s relation, Free length theory relation and their average deviation from experimental values of speed of sound have been calculated. The FT-IR spectra’s of pure components and their binaries at three different composition (v/v) 1:4, 1:1 and 4:1 have been measured at 298.15 K for interpretation of intermolecular interaction between molecules of binary liquid mixtures. The results revealed negative values for deviation in molar refraction (ΔRm), deviation in isentropic compressibility (Δks) and positive value for deviation in refractive index (ΔnD), deviation in speed of sound (Δu) and deviation in acoustic impedance (Δz). The results support the idea that strong interactions occur between molecules of binary mixtures. All the computed results were fitted with the Redlich–Kister type polynomial equation.

Introduction

It is very difficult to estimate the importance of intermolecular interaction forces in nature because the world would be a uniform ideal gas in absence of intermolecular interactions. The proper knowledge of mixing properties such as deviation in refractive index, deviation in speed of sound and other properties related to them are necessary to understand the molecular interactions between the components of binary mixtures [1], and also play important role in designing various chemical processes such as geometry at equilibrium position, the binding energy, characteristic spectra, ion exchange systems, gas adsorption solvents, mass transfer phenomena etc [2], [3], [4]. Various electrostatic interaction forces such as dipole-dipole forces, hydrogen bonding and repulsive forces play important role in biological systems such as DNA, RNA etc [5].

N-formylmorpholine which is used as a one of the main component of binaries in the present study plays important role for various industrial processes. Because of its specific nature of N-formylmorpholine is polar and dense solvent having good stability, it is widely used in extractive distillation of pure monocyclic aromatic hydrocarbons from petroleum feed stocks [6]. Halobenzenes are known for their higher electro negativity and are widely used in industries as nucleophilic reagents for synthesis processes. So the information related to deviation of physical properties such as density, viscosity, refractive index, speed of sound etc plays an important role for understanding behavior of components in binary and ternary mixtures.

In this present study, we report accurate data of refractive index and speed of sound for three binary mixtures, viz, N-formylmorpholine, + fluorobenzene, + chlorobenzene, + bromobenzene at temperature from 303.15, 308.15 and 313.15 K. Deviations in properties like nD, ΔRm, Δu, Δks and Δz are also reported. To understand more about these mixtures and their interaction behavior with each other, many theoretical relations of refractive indexes and speed of sound are also applied. The FT-IR study has been carried out for understanding inter or intra molecular hydrogen bonding between these binary mixtures.

Section snippets

Materials

In this present study, all organic liquid components use were of AR grade and were supplied by reputed companies. N-formylmorpholine (99.5% pure, supplied by Himedia chemical, India) and halobenzenes like fluorobenzene, chlorobenzene and bromobenzene (99.5% pure, supplied by S.D. fine chemicals, India) were used after purification using standard methods [7], [8] and their purity was confirmed by gas chromatography, which showed that the mass fraction purity was higher than 99.95%. The suppliers

Deviation in refractive index (ΔηD) and molar refraction (ΔRm)

Experimentally obtained values of refractive indexes (ηD) of pure components and their binary mixtures at 303.15, 308.15 and 313.15 K are listed in Table 3. Deviation in refractive index (ΔηD) and deviation in molar refraction (ΔRm) are calculated using following equations and their values are also listed in Table 3.ΔnD=nDexp(nD1ϕ1+nD2ϕ2)ΔRm=Rmexp(Rm1ϕ1+Rm2ϕ2)where, ϕ1, ϕ2; nD1,nD2 and Rm1,Rm2 are volume fraction, refractive index and molar refraction of components 1 and 2 respectively. ϕi,

Conclusion

The refractive index (ηD), speed of sound (Δu) are experimentally measured at 303.15, 308.15 and 313.15 K for whole composition range. Using these values, various deviation properties like deviation in refractive index (ΔηD), deviation in molar refraction (ΔRm), deviation in speed of sound (Δu), deviation in isentropic compressibility (Δks and Δksa) and deviation in acoustical impedance (Δz) have been calculated. Moreover nine theoretical refractive index calculating relations like Arago–Biot

References (53)

  • I.G. Kaplan

    Intermolecular Interactions: Physical Picture, Computational Methods and Model Potentials Intermolecular Interactions

    (2006)
  • T.A. Salman et al.

    Thermodynamic properties of the binary and ternary systems containing N-formylmorpholine methanol, benzene and toluene at 298.15 K

    J. Al-Nahrain Univ.

    (2011)
  • J.A. Riddick et al.

    Organic Solvents: Physical Properties and Method of Purification

    (1986)
  • A.I. Vogel

    Vogel’s Textbook of Practical Organic Chemistry

    (1989)
  • V. Campos et al.

    Density viscosity, refractive index, excess molar volume, viscosity, and refractive index deviations and their correlations for the (formamide + water) system, isobaric (vapor + liquid) equilibrium at 2.5 kPa

    J. Chem. Eng. Data

    (2008)
  • P. Brocos et al.

    Refractive indices, molar volumes and molar refractions of binary liquid mixtures: concepts and correlations

    Phys. Chem. Chem. Phys.

    (2003)
  • J.B. Biot, F. Arago, Memory on the affinities of bodies for light: and particularly on the strengths of the different...
  • T.P. Dale et al.

    On the influence of temperature on the refraction of light

    Phil. Trans. R. Soc. Lond.

    (1858)
  • H.A. Lorentz

    On the relationship between the propagation of light and mass density

    Wied. Ann. Phys.

    (1880)
  • J.F. Eykman, A.F. Holleman, Research refractometers, De Erven Loosjes,...
  • O. Weiner

    Theory of refraction constants

    Berichte (Leipzig)

    (1910)
  • W. Heller

    The determination of refractive indices of colloidal particles by means of a new mixture rule or from measurements of light scattering

    Phys. Rev.

    (1945)
  • G. Oster

    The scattering of light and its applications to chemistry

    Chem. Rev.

    (1948)
  • H. Eyring et al.

    Significant Liquid Structures

    (1969)
  • S. Sharma et al.

    Volumetric viscometric and ultrasonic studies on binary mixtures of oleic acid with alkyl esters at 303.15, 308.15 and 313.15 K

    Int. J. Phys. Sci.

    (2012)
  • J.A. Al-Kandary et al.

    Physicochemical properties for binary mixtures of anisole with 1-hexanol 1-heptanol, 1-octanol, 1-nonanol, and 1-decanol at 298.15, 303.15, 308.15, and 313.15 K

    Chem. Eng. Comm.

    (2008)
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