TECHNOLOGY FOCUS - ORGANIC CHEMISTRY - Preferred Components: The second distillation column operates 0.1-100 kPa, preferably 0.1-35 kPa. Preferred Components: The total concentration of water fed to the second column is less than 10 wt.% (preferably 2-6 wt.%), based on the total weight of all components fed to the second column. In the process, an extractive agent comprising water is fed to the second column. The first distillate comprises less than 10 wt.% water. The second distillate comprises less than 30 wt.% of ethanol. The second residue comprises less than 100 wppm ethyl acetate. The acetic acid conversion in the reactor is greater than 90%. Preferred Method: The water is removed from the first distillate using an adsorption unit, membrane, and/or extractive column distillation, to yield an ethanol mixture stream comprising less than 10 wt.% water. The acetic acid is formed from methanol and carbon monoxide, where each of the methanol, the carbon monoxide, and hydrogen for the hydrogenating step is derived from syngas, and the syngas is derived from a carbon source comprising natural gas, oil, petroleum, coal, and/or biomass. The process comprises: providing a crude ethanol product comprising ethanol, ethyl acetate, acetic acid, and water, the first separating step, and the second separating step. EXAMPLE - A crude ethanol product was separated in a first column into a first distillate comprising ethanol (57.6 wt.%), ethyl acetic acid (15.1 wt.%) and water (24.7 wt.%) and a first residue. The first distillate was sent to a second column, which formed a second distillate comprising ethanol (12.4 wt.%), ethyl acetic acid (76 wt.%) and water (5.1 wt.%) and a second residue (comprising (in wt.%): ethanol (67.6) and water (30.8)), under an atmospheric pressure and demonstrated significant amounts of ethanol in the second distillate to remove water from the first distillate. A first distillate comprising ethanol and ethyl acetate from a first column was introduced to a second column. The light ends column, e.g., second column, was operated at a pressure of 35 kPa. The second residue was controlled to maintain an ethyl acetate concentration of less than 100 wppm. By varying the water concentration that was fed to the column, an energy reduction was realized. A comparison was conducted by feeding a first distillate with the same composition through a second column that operated at a pressure of 101 kPa. less energy was required to separate ethanol and ethyl acetate when the second column was run at reduced pressure, i.e. 35 kPa, that increased in water percentage in the feed did not increase the amount of energy required to separate ethanol and ethyl acetate. Further separation of water from the second residue accomplished by using an adsorption unit or membrane and worked up to obtain the ethanol.