The development of techniques suitable for on-line analysis of gas-phase molecular sodium species, resulting from the combustion and gasification of low-rank coals is described. In particular two techniques have been demonstrated, these are: (a) laser-induced photofragment fluorescence and (b) microwave spectroscopy. The photofragment technique can be applied in situ and yields excellent detection limits (< 0.1 ppb of NaCl and 1 ppb NaOH) with good discrimination between the two major gas-phase species - NaCl and NaOH. Limitations of this technique include absorption of the ultraviolet (UV) photolysis excitation by other chemical species and particulates. Microwave spectroscopy shows promise in determining the sodium species distribution in the gas-phase. A purpose built analytical instrument (known as MILLIJET HT) is being developed for application in high-temperature environments. Early results indicate detection limits of < 100 ppb NaCl. Lack of sensitivity for NaOH is being attributed to the formation of NaOH dimers and larger clusters. Detailed calculations of the dimer structure and the dimer-monomer reaction have been undertaken in order to maximise the performance of the instrument.