The solidification of Si-As alloys induced by pulsed laser melting was studied at regrowth velocities where the partition coefficient is close to unity. The congruent melting temperatures, TO, of Si-As alloys were determined using a temperature measurement technique developed for this work, and were confirmed with TOmeasurements using three other methods. The time-resolved temperature measurement uses a thin-film platinum thermistor, below and electrically isolated from the Si-As alloy layer, to directly measure the temperature during solidification. This, combined with measurements of transient conductance of the Si-As alloy, time-resolved reflectivity and Rutherford Backscattering Spectrometry, permitted the determination of the solid-liquid interface temperature, velocity and partition coefficient, the latent heat of fusion and TO for Si - 4.5 at. % As and Si - 9 at. % As alloys.