Methods for separation of two optical isomers in a racemate into its constituent isomers by statistical means are described, whereby the saturated racemate solution is first allotted into small samples by means of microfluidic or inkjet techniques to obtain small sample quantities (picoliters to microliters) with one isomer in measurable excess of the other. The samples are then tested by means of spectrophotometers used for measuring Cotton Effects or Circular Dichroism or other related effects which measure the difference in the absorption of right and left circularly polarized light, so that there is a predetermined minimum excess of one enantiomer. Collecting them in three different receptacles then separates the three types of samples. The right and left excess samples are then used in the crystallization process to obtain right or left handed isomers respectively. The third type of sample that is collected is again re-circulated through the sampling process so that right and left excess samples are collected again out of the neutral samples (with less than minimum excess of one kind or the other) and the process continued to crystallize out the two isomers.