Modern thermodynamic models indicate that fluids consisting of complex molecules may display non-classical gasdynamic phenomena such as rarefaction shock waves (RSWs) in the vapour phase. Since the thermodynamic region in which non-classical phenomena are physically admissible is finite in terms of pressure, density and temperature intervals, the intensity of RSWs is expected to exhibit a maximum for any given fluid. The identification of the operating conditions leading to the RSW with maximum intensity is of paramount importance for the experimental verification of the existence of non-classical phenomena in the vapour phase and for technical applications taking advantage of the peculiarities of the non-classical regime. This study investigates the conditions resulting in an RSW with maximum intensity in terms of pressure jump, wave Mach number and shock strength. The upstream state of the RSW with maximum pressure drop is found to be located along the double-sonic locus formed by the thermodynamic states associated with an RSW having both pre-and post-shock sonic conditions. Correspondingly, the maximum-Mach thermodynamic and maximum-strength loci locate the pre-shock states from which the RSW with the maximum wave Mach number and shock strength can originate. The qualitative results obtained with the simple van der Waals model are confirmed with the more complex StryjekVeraPengRobinson, MartinHou and SpanWagner equations of state for selected siloxane and perfluorocarbon fluids. Among siloxanes, which are arguably the best fluids for experiments aimed at the generation and measurement of an RSW, the state-of-the-art SpanWagner multi-parameter equation of state predicts a maximum wave Mach number close to 1.026 for D₆ (dodecamethylcyclohexasiloxane, [O-Si-(CH₃)₂] ₆). Such value is well within the capacity of the measurement system of a newly built experimental set-up aimed at the first-ever demonstration of the existence of RSWs in dense vapours.

In the vapour phase and close to the liquid-vapour saturation curve, fluids made of complex molecules are expected to exhibit a thermodynamic region in which the fundamental derivative of gasdynamic Γ is negative. In this region, non-classical gasdynamic phenomena such as rarefaction shock waves are physically admissible, namely they obey the second law of thermodynamics and fulfil the speed-orienting condition for mechanical stability. Previous studies have demonstrated that the thermodynamic states for which rarefaction shock waves are admissible are however not limited to the Γ < 0 region. In this paper, the conditions for admissibility of rarefaction shocks are investigated. This results in the definition of a new thermodynamic region - the rarefaction shocks region - which embeds the Γ < 0 region. The rarefaction shocks region is bounded by the saturation curve and by the locus of the states connecting double-sonic rarefaction shocks, i.e. shock waves in which both the pre-shock and post-shock states are sonic. Only one double-sonic shock is shown to be admissible along a given isentrope, therefore the double-sonic states can be connected by a single curve in the volume-pressure plane. This curve is named the double sonic locus. The influence of molecular complexity on the shape and size of the rarefaction shocks region is also illustrated by using the van der Waals model; these results are confirmed by very accurate multi-parameter thermodynamic models applied to siloxane fluids and are therefore of practical importance in experiments aimed at proving the existence of rarefaction shock waves in the single-phase vapour region as well as in future industrial applications operating in the non-classical regime.