If there are no non-condensable gases, the vapor space will be at the temperature of the liquid and its pressure will correspond to vapor pressure of the liquid. It's composition can be found from a bubble point calculation of the liquid.
If non-condensible gases are present (e.g., air), the liquid will exert a partial pressure in the gas phase:
PP = sum(xi*VPi*gammai),
where PP=partial pressure of all condensibles, xi=component i liquid phase mole fraction, VPi=component i vapor pressure at liquid phase temperature, and gammai=component i activity coefficient in the liquid phase. The summation is taken over all components in the liquid phase.
The difference between the vessel pressure and PP will be made up by the non-condensible gas.