The diffusion coefficients of seven octane isomers in helium were measured by the chromatographic broadening technique with excellent precision and a n estimated accuracy of 1%. This was accomplished by computer manipulation of the data. It is found that as branching increases, the diffusion coefficients also increase. This can be explained by Giddings' shielding treatment. A direct correlation is found between the diffusion coefficients of the isomers and their critical volumes and related parameters. Data analysis indicates that the critical volume of 2,2,4-trimethylpentane quoted in the literature might be too high. An attempt is made to modify the Fuller, Schettler, and Giddings estimating equation to take into account molecular branching.Mass transport phenomena play a major role in many and diverse fields of both basic and practical science. For example, diffusion is important in chemical reactions and in designing absorbers, distillation columns, etc. Two excellent reviews by Mason and Marrero1,2 recently appeared which contained both a theoretical treatment of diffusion and a discussion of experimental diffusion measurements. There are many equations which attempt to (15)