Advances in Chemistry Research, Volume 8 by James C. Taylor

By James C. Taylor

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AIMS AND BACKGROUNDS The aim of this work is a study of electronic structure of molecular insectitsid DDT and theoretical estimation its acid power by quantum-chemical method AB INITIO in base 6311G**. The calculation was done with optimization of all parameters by standard gradient method built-in in PC GAMESS [1]. ru 48 V. A. Babkin, V. U. Dmitriev and G. E. Zaikov molecule in gas phase. Program MacMolPlt was used for visual presentation of the model of the molecule. [3]. METHODICAL PART Geometric and electronic structures, general and electronic energies of molecular insectitsid DDT was received by method AB INITIO in base 6-311G** and are shown on figure 1, and in table 1 .

Equations (2) and (3) when combined with a constitutive kinetic equation in which the rate of approach to equilibrium is proportional to the departure from equilibrium, are sufficient to describe the response of a glass to any thermal history. The intention, here, is to evaluate the apparent activation energy Δh*, introduced in (2), in order to estimate the effect of the copolymer composition on the relaxation processes. In this respect, a set of experiment in which the sample is cooled at different constant rates before immediately scanning in DSC is required.

Enthalpy Relaxation The procedure adopted here for the analysis of DSC data follows a well-recognized approach. It is assumed that the relaxation time(s) (τ ) for enthalpy relaxation depends on both Thermal Bhaviour and Enthalpy Relaxation in Aromatic Polycarbonate… 33 the temperature (T) and the structure of the glass, identified by its fictive temperature (Tf), according to the so called Tool-Narayanaswamy-Moynihan (TMN) equation [15]: ⎡ xΔh * (1 − x)Δh * ⎤ + τ (T , T f ) = τ 0 exp⎢ ⎥ RT f ⎥⎦ ⎢⎣ RT (2) where τ0 is the value of τ in equilibrium at infinitively high temperature, Δh* is the apparent activation energy for enthalpy relaxation, and x (0≤x≤1) is the non-linearity parameter identifying the relative contributions of temperature and structure to the relaxation(s) time.

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