The existence of NaCl in the vapor phase of post-combustion gases was confirmed in a laboratory study utilizing size-classified samples of six coals with varying chlorine concentrations. Laser induced photodissociation and fluorescence was used to successfully detect molecular sodium chloride vapor levels in coal combustion gases at 1200 K. Results obtained from combustion of a high chlorine Loy Yang coal yielded a linearly increasing fluorescence signal with increasing coal particle feed rate. Under comparable combustion conditions, relative measurements obtained upon combustion of live U.S. coals with differing chlorine contents yielded normalized NaCl signal intensities strongly dependent on coal type. Results were found to increase with increasing total chlorine content of the parent coals: for the U.S, coals, results directly scaled with chlorine level within the bounds of experimental error. This dependence on chlorine level was confirmed by equilibrium calculations at both the dilute conditions of the experiments and at realistic post-flame oxygen concentrations. Kinetic calculations for the sodium/chlorine/oxygcn/ hydrogen system indicated that steady state would be achieved rapidly under the conditions of these experiments. © 1992, Taylor & Francis Group, LLC. All rights reserved.