Ultrasonic Studies on Charge Transfer Complexes of Cyclo Alkanones with Chloroform in n-Hexane Solutions

Authors: Kannappan V.¹; Santhi R.J.¹; Malar E.J.P.²

Source: Physics and Chemistry of Liquids, Volume 40, Number 4, 1 January 2002 , pp. 507-525(19)

Publisher: Taylor and Francis Ltd

Abstract:

The ultrasonic velocity (U), density () and viscosity () of solutions containing equimolar concentration of four cycloalkanones (cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone) and chloroform in n-hexane solutions have been measured in the temperature range 293-313 K. Acoustical parameters such as adiabatic compressibility (), Rao constant (R), absorption coefficient (/f²), free energy of activation (G*), internal pressure (_i) cohesive energy (CE), free volume (V_f), interaction parameters with respect to ultrasonic velocity (X_u), density (X), and viscosity (X) were calculated from the experimental data. These investigations indicate the formation of charge transfer complexes between cyclic ketones and chloroform in n-hexane medium. Formation constant values of the complexes have been evaluated using a newly proposed equation. Thermodynamic parameters such as free energy change (G), enthalpy change (H), and entropy change (S) for the formation of these complexes are computed from the variation of formation constant values with temperature. The stability constants of the charge transfer complexes formed between four cyclic ketones and chloroform correlate satisfactorily with polarisability (), and ionization potential (IP) values of the ketones computed by semi empirical molecular orbital calculations.

Keywords: Ultrasonic velocity; Thermodynamic parameters; Charge transfer complexes; Cyclo alkanones; Chloroform

Document Type: Research article

Affiliations: 1: Post-Graduate and Research Department of Chemistry, Presidency College, Chennai - 600 005, India 2: Department of Physical Chemistry, University of Madras, Guindy Campus, Chennai - 600 025, India

Publication date: 2002-01-01

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