A computer model based on the Gibbs energy minimization principle was used to identify and quantify chlorine (Cl)- and alkali-containing species formed in the temperature range from 1100 to 1200 K, air/coal ratio of 1.0 and 1.1 and Ca/S ratio varying from 0 to 2.5 using low and high Cl content coals. HCl, KCl and NaCl were the major Cl-containing volatile compounds. The amount of HCl in the vapor phase decreased and that of KCl and NaCl increased with increasing Ca/S ratio from 0 to 2.5, whereas the increase in the air/coal ratio from 1.0 to 1.1 had the opposite effect. KCl and NaCl were the major, and KOH, NaOH, K2SO4 and Na2SO4 the minor alkali-containing species in the vapor phase of all the cases analyzed. The amount of all alkali metal-containing compounds increased with increasing Ca/S ratio and decreased with increasing air/coal ratio from 1.0 to 1.1. For the low Cl coal, the relative contribution of KOH and NaOH to the overall alkali emissions was greater than that for the high Cl coal. (C) 2002 Elsevier Science B.V. All rights reserved.