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

الموضوعات : Journal of Physical & Theoretical Chemistry

M. Khaleghian ¹ , Gh. R. Ghashami ²

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تاريخ الإرسال : 16 الثلاثاء , رجب, 1436 تاريخ التأكيد : 16 الثلاثاء , رجب, 1436 تاريخ الإصدار : 16 الثلاثاء , رجب, 1436

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

ملخص المقالة :

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.