It has recently been discovered that, when subjected to moderate amounts of pressure, methane dissolves in water to form binary mixtures of up to 40% molar methane. No significant solubility of water in methane is known. In these mixtures, the water hydrogen-bond network is largely complete and surrounds the methane molecules. The discovery of this dense mixture has once again highlighted the technical difficulties involved in accurately describing and sampling mixing phenomena both computationally and experimentally. Here, we present a systematic and critical study of the methods employed to characterize binary mixtures and their robustness. This study highlights the requirements needed to develop a quantitative understanding, and it proposes new and more accessible measures of miscibility to investigators, particularly for in silico analysis.