In spectrochemistry, various plasma sources are used for the analysis of samples. The simplest way to characterise these plasma sources is to determine the absolute intensities of several atomic lines of the main plasma gas (argon or helium). From these measurements absolute population densities of excited states can be deduced and, via a so-called Boltzmann plot, the electron temperature Te and density ne. This method works quite well as long as the plasma is relatively close to equilibrium. The reason why spectrochemical plasmas can show strong deviations from equilibrium will be discussed. An other limitation of emission spectroscopy is the lack of accurate transition probabilities for transitions from highly excited states. For argon 15 of these probabilities have been determined with an uncertainty of ±25%.