In the de-novo synthesis and formation of PCDD/PCDF, the transfer of inorganic chlorine to the carbonaceous material of fly ash plays an important role. Here, copper acts as a catalyst in the chlorination reaction. In experiments in the range of 250-350 degrees C under helium, we determined the stoichiometry of the chlorination reaction with model systems. Therefore, it was necessary to develop a method to quantify the copper(II) and copper(I) ions. In a combination of solid electron paramagnetic (spin) resonance spectroscopy (EPR) for Cu(I), and X-ray fluorescence spectroscopy (XRFA) analysis for Cu (total), we found a way for the quantification of copper(I) and (II). With these experiments, we can show that the chlorination reaction is relatively fast and comes to a stop under helium, after the copper(II) is reduced. The ratio between the organic chlorine formed and copper(II) reduced is, at the end of the reaction, 0.5, which is in agreement with the following reaction: 2CuCl2 + R-H-->2CuCl + R-Cl + HCl.