The purpose of the present work was to investigate the effect of the concentration of HI and reaction time in the chemical desulfurization of Cayirhan lignite in a microwave energy set up and to compare the results with those obtained in a thermal heating system. As the concentration of the HI was increased, the extent of desulfurization was also increased in all the experiments done for all of the samples of lignite. The main difference between the thermal and microwave heating was the extremely short times for desulfurization in the case of microwave experiments. After desulfurization experiments S-total/C ratio of all of the samples decreased to a lower value than that of the raw lignite which was 0.034. The loss of the sulfur containing bands in the FTIR spectra of the desulfurized lignite showed that the HI treatment was effective in the cleavage of dithioethers and thioetheric groups. Sulfur containing functionalifies like thioethers and thiols although usually requiring strong reducing agents could be removed in significant amounts with concentrated hydroiodic acid from the coal matrix. The rapidity of the desulfurization reactions with microwave heating in concentrated HI was probably due to localized superheating which made HI more effective in the reactions such as with thioethers and thiols that normally resisted to cleavage by HI under thermal heating conditions. (C) 2002 Elsevier Science Ltd. All rights reserved.