That depends on the pressure. If the pressure is 101.325 kPa, then it would not be pure. But it could still be pure and boil at 101ºC if the pressure where very slightly higher than 101.325 kPa, i.e. at 103.4 kPa.
The 100 degree mark is for water is subject to air pressure at sea level, As altitude increases, both air pressure and the boiing point decrease. We lived in Colorado at 7200 ft above sea level- water there boils at 198 F, 92 C.
100C is at sea level. Water boils at different temperatures based on the altitude you are at. Atlanta is 738 to 1050 feet in elevation. In Denver Co. at 5,280 feet you will find it boils at far less than 100C.
The boiling point of pure ethanol is 78 degrees Celsius and the boiling point of water is 100 degrees Celsius. The mixture boils at 87 degrees Celsius and the vapor above the boiling solution should be less dilute, more potent, but not pure ethanol.