The refined diagnostic information obtainable by high-order spectrometry is illustrated by the results of quantitative measurements of a few rotational lines of OH in the ultraviolet spectrum of water-vapor plasmas generated in a wall-stabilized arc. Because of the high spectral and spatial resolution achieved in end-on measurements, the emission and also the absorption coefficients pertaining to homogeneous arc regions were obtained directly from measured line spectra—although the absorption was not measured explicitly—leading to the occupation of the upper and the lower state for the transition. The gas temperature was determined from the halfwidth of the Doppler-broadened rotational lines. The measured resolving power of the spectrometer was of the order of 400,000 in these measurements.