Granular silicon dioxide is placed in a treatment chamber which is heated to a temperature ranging from 700.degree. to 1300.degree. C. The chamber is then rotated for a prescribed period of time to mix the grains while a gaseous atmosphere of chlorine and/or hydrogen chloride is passed through the treatment chamber. The mixing period is followed by a resting period which is at least ten times longer than the mixing time. During the resting period the grains are exposed to a constant electric field having a strength of 600 to 1350 V/cm applied across the chamber. The foregoing cycle is repeated several times. For working the process a device is used which includes a quartz glass rotary tube into which hollow silicon carbide electrodes extend.