Statistical mechanics and transition state (TS) theory describe rates and selectivities of C-C bond cleavage in C-2-C-10 n-alkanes on metal catalysts and provide a general description for the hydrogenolysis of hydrocarbons. Mechanistic interpretation shows the dominant role of entropy, over enthalpy, in determining the location and rate of C-C bond cleavage. Ir, Rh, and Pt clusters cleave C-C bonds at rates proportional to coverages of intermediates derived by removing 3-4 H-atoms from n-alkanes. Rate constants for C-C cleavage reflect large activation enthalpies (Delta H double dagger, 217-257 kJ mol(-1)) that are independent of chain length and C-C bond location in Ce4+ n-alkanes. C-C bonds cleave because of large, positive activation entropies (Delta S double dagger, 164-259 J mol(-1) K-1) provided by H-2 that forms with TS. Kinetic and independent spectroscopic evidence for the composition and structure of these TS give accurate estimates of Delta S double dagger for cleavage at each C-C bond. Large differences between rate constants for ethane and n-decane (similar to 10(8)) reflect an increase in the entropy of gaseous alkanes retained at the TS. The location of C-C bond cleavage depends solely on the rotational entropies of alkyl chains attached to the cleaved C-C bond, which depend on their chain length. Such entropy considerations account for the ubiquitous, but previously unexplained, preference for cleaving nonterminal C-C bonds in n-alkanes. This mechanistic analysis and thermodynamic treatment illustrates the continued utility of such approaches even for hydrogenolysis reactions, with complexity seemingly beyond the reach of classical treatments, and applies to catalytic clusters beyond those reported here (0.6-2.7 nm; Ir, Rh, Pt).