The X-ray Kβ emission spectra from molecular gases is discussed with the use of a particular example, CH3Cl. With the help of a crude threshhold experiment, the multiple vacancy processes are shown to be on the high energy side of the prominent spectral lines in Cl Kβ emission from CH3Cl. From a recent molecular orbital calculation, the Cl Kβ molecular emission lines are identified as the 3 e and 7 a1 orbitals of CH3Cl. The valence K emission spectra can be interpreted for the most part in terms of one electron single vacancy transitions from inner shells to the various outer molecular orbitals, where the spectral line position and intensity are dependent on the molecular term value, symmetry and orbital overlap. In the course of extending the X-ray molecular emission studies to the L series of sulphur and chlorine we measured the L23 spectra from argon gas to study the instrumental response in this region. A prominent extra low energy emission feature was found in the Ar L23 spectra. A similar feature is also observed in the L23 emission of Cl and K from KCl. These extra features are interpreted as evidence of a double electron process