When a porous solid consists of discrete particles it is inconvenient to describe the outer boundary of the particles as the external surface.
Sources:
PAC, 1972, 31, 577. 'Manual of Symbols and Terminology for Physicochemical Quantities and Units, Appendix II: Definitions, Terminology and Symbols in Colloid and Surface Chemistry' on page 585 (https://doi.org/10.1351/pac197231040577)
PAC, 1976, 46, 71. 'Manual of Symbols and Terminology for Physicochemical Quantities and Units - Appendix II. Definitions, Terminology and Symbols in Colloid and Surface Chemistry. Part II: Heterogeneous Catalysis' on page 79 (https://doi.org/10.1351/pac197646010071)