The chemical equilibria of acetals of acetaldehyde reactive systems (with methanol, ethanol, and n-butanol to form 1,1-dimethoxyethane, 1,1-diethoxyethane, and 1,1-dibuthoxyethane, respectively) were studied in the temperature range (293-333 K) in the liquid phase. The three reactive systems exhibit a strong nonideal behavior in the liquid phase. The knowledge of the activity coefficients is required to obtain the thermodynamic equilibrium constants K-a. The activity coefficients were estimated by the modified UNIFAC method, which already includes the parameters for the acetal group. The reaction enthalpies for the three acetalizations in the liquid phase were obtained from the temperature dependences of the corresponding thermodynamic equilibrium constants. These values were compared to those obtained by high-level ab initio calculations of the reaction participants using the Gaussian 03 program package. Absolute electronic energy values of the molecules have been obtained using G3(MP2) level. Using these results, calculated equilibrium constants and enthalpies of reaction of the acetals synthesis in the liquid phase based on the principles of statistical thermodynamics are found to be in acceptable agreement with the data obtained from the thermochemical measurements.