{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,23]],"date-time":"2026-10-23T20:49:58Z","timestamp":1792788598097,"version":"4.5.0"},"reference-count":197,"publisher":"MDPI AG","issue":"4","license":[{"start":{"date-parts":[[2026,2,10]],"date-time":"2026-02-10T00:00:00Z","timestamp":1770681600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006537","name":"Campus France","doi-asserted-by":"crossref","id":[{"id":"10.13039\/501100006537","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Near-critical and supercritical carbon dioxide (SC-CO2) is extensively utilized in high-pressure separation, extraction, polymer processing, and carbon capture and utilization (CCU) technologies owing to its tunable density, low viscosity, high diffusivity, and environmentally benign nature. Reliable phase equilibrium data are indispensable for process design and optimization, especially in the near-critical region characterized by pronounced non-idealities, high compressibility, and density fluctuations. This review synthesizes experimental phase behaviour studies for binary mixtures of CO2 with diverse components, including hydrocarbons, alcohols, ethers, esters, ketones, water, monomers\/polymers, ionic liquids (ILs), and deep eutectic solvents (DESs), compiling extensive vapour\u2013liquid equilibrium (VLE), liquid\u2013liquid equilibrium (LLE), and critical data across industrially relevant pressure (up to 40 MPa) and temperature (up to 400 K) ranges. It critically evaluates analytical (sampling and non-sampling) and synthetic methodologies, addressing challenges in CO2-rich phase handling, depressurization artefacts, and near-critical phenomena, while assessing data consistency against established reliability criteria. Key trends emerge, such as enhanced solubility with increasing pressure and CO2 density, chain-length dependencies in hydrocarbons and alcohols, and Lewis acid\u2013base interactions driving solvation in polar systems. The review highlights gaps in multicomponent data and proposes integrating high-quality experiments with advanced thermodynamic modelling to enhance predictive accuracy. Future directions emphasize high-precision in situ techniques, expanded datasets for complex mixtures, and novel CO2-philic solvents to advance sustainable SC-CO2 applications.<\/jats:p>","DOI":"10.3390\/molecules31040614","type":"journal-article","created":{"date-parts":[[2026,2,11]],"date-time":"2026-02-11T11:13:15Z","timestamp":1770808395000},"page":"614","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Phase Behaviour of Binary Mixtures Involving Near-Critical and Supercritical Carbon Dioxide\u2014A Review"],"prefix":"10.3390","volume":"31","author":[{"given":"Pradnya","family":"Ghoderao","sequence":"first","affiliation":[{"name":"UCP, ENSTA Paris, Institute Polytechnique de Paris, 828 Boulevard des Mar\u00e9chaux, 91762 Palaiseau, France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4028-7133","authenticated-orcid":false,"given":"Patrice","family":"Paricaud","sequence":"additional","affiliation":[{"name":"UCP, ENSTA Paris, Institute Polytechnique de Paris, 828 Boulevard des Mar\u00e9chaux, 91762 Palaiseau, France"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,2,10]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"133","DOI":"10.1016\/j.jsm.2017.02.001","article-title":"Analysis of greenhouse gas emissions in the European Union member states with the use of an agglomeration algorithm","volume":"15","author":"Kijewska","year":"2016","journal-title":"J. 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