The structure of normal shock waves is considered when the ratio of molecular masses mp/m of a binary mixture of inert monatomic gases is large and the density ratio ρp/ρ is of order unity or below. Generalized hydrodynamic equations, valid for arbitrary intermolecular potentials, are obtained from a hypersonic closure of the kinetic equation for the heavy gas and a near-equilibrium closure for the light component. Because the Prandtl number of the light gas and the Schmidt number of the mixture are nearly constant, the only independent transport coefficient arising in the model is the viscosity μ of the light gas, which is absorbed into a new independent position variable s. Knowledge of μ as a function of temperature thus determines the shock structure independently from the details of the intermolecular potential, allowing comparison with experiments in the complete absence of free parameters. In terms of the ratio M (frozen Mach number) between the speed of propagation and the sound speed of the light gas in the unperturbed medium, one finds that: (i) When M > 1, the behaviour is similar to that of a ‘dusty gas’, with a broad relaxation layer (outer solution) following a sharp boundary layer through which the speed of the heavy gas is almost constant (a shock within a shock). (ii) When (1 + ρp/ρ)s−½ < M < 1, the boundary layer disappears, yielding a so-called ‘fully dispersed wave’. (iii) Because the internal energy of the heavy gas is negligible, the present problem differs from previous shock studies in that, for the first time, the structure of the relaxation region is obtained algebraically in phase space, thus permitting an exhaustive study of the behaviour. From it, the overshooting solution found by Sherman (1960) is related to the unphysical degenerate branch of the outer solution arising when M > 1, showing a failure of the Chapman–Enskog theory, even for weak shocks, when the heavy gas is dilute. Also, an algebraic explanation arises for the ‘double hump structure’ observed in He–Xe shocks. (iv) When M is nearly unity, the initial boundary layer spreads out, and the structure must be obtained by integration of a numerically unstable system of three differential equations. However, the reduction of order brought about by the weak variation of the light-gas entropy at the head of the shock, results in a stable system of equations that we integrate numerically. Excellent phase-space agreement with recent shock-tube experiments of Tarczynski, Herczynski & Walenta (1986) is found for both weak and strong shocks.