A free-burning arc experiment was performed in a gas mixture composed of CO2 /O2 /C5F10O (85% / 10% / 5%). An optical emission spectroscopy diagnostic was developed to obtain spatially resolved arc spectra at a high frame-rate. Spectral measurements are compared with simulated spectra to estimate arc parameters including temperature and composition. These techniques are used to characterize the arc and its associated electrode jets over a range of conditions, in order to study the influence of ablated Cu/W on arc characteristics. The observed spectra indicate that the ablation of the contact tip primarily occurs through vaporization rather than the expulsion of droplets. The metal vapor content of the arc is investigated as the arc driving current is varied, and a transition threshold for increased ablation at electrode current densities above 50A/mm² is determined. The expansion angle of the electrode jet is estimated from the concentration of metal vapor in the arcing region at different axial positions, using a basic conical expansion model. The dependence of the measured voltage on the arc composition is examined, and a positive correlation between Cu content and arc voltage is identified. This trend is attributed to the higher emissivity of the metal vapor, which suppresses the central arc temperature and increases its resistivity.