A rapid method is provided for the on-line determination of sodium sulfide concentration and/or percent sulfidity in green liquors or smelt solutions used for the production of either kraft or sulfite pulp. The method eliminates manual sampling, and the need for frequent equipment maintenance. The method includes the steps of withdrawing samples of a smelt solution or green liquor from the kraft or sulfite manufacturing process, subjecting the samples to near-infrared spectrophotometry over a predetermined range of wave numbers so as to produce absorbance measurements relative to a reference spectrum of either water or a caustic soda-sodium carbonate solution, determining the absorbance shown by different combinations of sodium sulfide, sodium hydroxide, sodium carbonate and sodium chloride concentrations, correlating by multivariate calibration the relationships between the absorbance measurements of unknown samples and the absorbance shown by different combinations of sodium sulfide, sodium hydroxide, sodium carbonate and sodium chloride so that the amount of sodium sulfide and/or the percent sulfidity can be accurately determined for any levels of TTA or chloride present in the liquor.