The present study provides a detailed description of the dissipative structure of shock waves propagating in dense gases which have relatively large specific heats. The flows of interest are governed by the usual Navier–Stokes equations supplemented by realistic equations of state and realistic models for the density dependence of the viscosity and thermal conductivity. New results include the first computation of the structure of finite-amplitude expansion shocks and examples of shock waves in which the thickness increases, rather than decreases, with strength. A new phenomenon, referred to as impending shock splitting, is also reported.