ABSTRACT
The acid hydrolysis of formamide is studied in an extensive series ranging from pure water up to 75 percent by weight acetone at the temperature range 25-50 degree. A minimum is observed at 0.17 mole fraction of acetone. The reaction is found to be electrostatically independent and the results are discussed in the light of the role of water in the mechanism of the reaction and its structural chance in the mixed solvent. The thermodynamic properties of the activated complex are calculated and discussed in terms of the solvation effects
Subject(s)
Chemistry, PhysicalABSTRACT
The thermodynamic dissociation constant of p-nitro-anilinium ion pK[BH][+], was calculated in aqueous, -formamide, -acetamide and -propionamide solvent, it was found that the order of basicity of such mixtures is in agreement with the electron availability at the oxygen atom of the amide molecule. The calculated values of the free energy of transfer indicate that, the addition of the amide increases the basicity of water molecules. The equilibrium constant K'[b]of the equilibrium, H[3] O[+] [amide] [amide]. H[+] +H[2]O, is calculated which indicates that the basicity increases in the order formamide < acetamide < propionamide. The free energies of transfer delta Gt[0] [H+], of the solvated proton, from water to aqueous amide show that propionamide has a higher ability to replace a water molecule in the aquo-proton than formamide