Quantum mechanics investigation of acid dissociation constant of carboxylic acids in aqueous solution

محورهای موضوعی : Journal of Physical & Theoretical Chemistry

M. Khaleghian ¹ , Gh. R. Ghashami ²

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تاریخ دریافت : 1394/02/15 تاریخ پذیرش : 1394/02/15 تاریخ انتشار : 1394/02/15

کلید واژه: pKa, Acid dissociation constants, Free energy, Gas phase, solution, Thermodynamic&#x0D, &#x0D, cycles, Deprotonation,

چکیده مقاله :

According to the Bronsted definition, any compound which has a hydrogen atom is an acid, since itmay be lost as a proton. A thermodynamical cycle is proposed to calculate absolute pKa values forBronsted acids in aqueous solution. The equilibrium of dissociation of a Bronsted acid depends onthe interaction of the acid and its conjugate base with solvent molecules. There fore the pKa valuedepends on the solvent medium. The polarizable continuum model (PCM) was used to describe thesolvent, and absolute pKa values were computed for different compounds: HCOOH, CH3COOH,C6H5COOH, FCH2COOH and CH3CH2COOH. The model of furnishes pKa values was in goodagreement with the experimental results for some classes of compounds. The quantum Mechanics(QM) calculations were carried out with the GAUSSIAN 98 program based on HF/6-31+G** level.