The sulfonation in 98.5% H2SO4at 25.0 °C of naphthalene-1-sulfonic acid yields 58% 1,5-, 32% 1,6-, and 10% 1,7-disulfonic acids and that of the 2-sulfonic acid 4% 1,3-, 74% 1,6-, 18% 1,7-, and 4% 2,6- + 2,7-disulfonic acids. Further sulfonation of the latter disulfonic acid mixture in 105.2% H2SO4at 25.0 °C yields 78% 1,3,6- and 12% 1,3,5- + 1,3,7-trisulfonic acids. Reaction of naphthalene-1,5-disulfonic acid with 105.2% H2SO4at 25 °C yields 5-sulfonaphthalene-1-sulfonic anhydride.Partial rate factors for the sulfonation of naphthalene-1- and -2-sulfonate in highly concentrated aqueous sulfuric acid (where the sulfonating entity is H2S2O7) are reported. They are discussed in terms of the difference in the reactivity of the α- and β-positions of the naphthalene skeleton and the electronic and steric effects of the sulfonate substituent already present.