{
  "abstract": "The Gibbs equation (∆ G = ∆ H – T ∆ S ) remains a cornerstone of chemical thermodynamics. Yet the scope and origins of the widely observed correlations between the enthalpies (∆ H ) and entropies (∆ S ), or Gibbs energies (∆ G ) and enthalpies, have long been debated. This study systematically analyzes over 4,500 experimental thermodynamic values at 298.15 K to establish quantitative principles governing the ∆ G vs. ∆ H relationship across solvation, vaporization, and molecular complexation processes. By classifying systems according to hydrogen-bonding capabilities, we demonstrate that non-associated solute–solvent pairs universally follow a baseline linear correlation (the Barclay–Butler line). Systematic deviations from this baseline are quantitatively attributed to distinct physical contributions: conformational flexibility in long-chain aliphatics (hindered internal rotation), a constant entropic penalty per directional hydrogen bond, and predominantly entropic solvophobic effects in associated solvents. Through thermodynamic transformations, these solvation/vaporization rules are extended to yield a universal linear ∆ G –∆ H relationship with an invariant slope of 0.660 for both solution- and gas-phase molecular complexation, encompassing hydrogen bonding, charge transfer, and dispersion interactions. The framework is successfully applied to α -cyclodextrin host–guest systems, where it can be used as a diagnostic tool for detecting anomalous or non-inclusion binding modes and for deeper analysis of the complexation mechanism. Ultimately, this work transforms the Gibbs equation into a predictive instrument, enabling accurate estimation of enthalpies from single-temperature Gibbs energy measurements and providing a unified, mechanism-independent foundation for analyzing intermolecular interactions in systems of varying complexity.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "name": "Boris N. Solomonov"
    },
    {
      "name": "Mikhail I. Yagofarov",
      "orcid": "0000-0003-4970-4917"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/1rk2tbfwgyezt.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15006218/v2",
  "fulltext_url": null,
  "id": "1rk2tbfwgyezt",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15006218/v2",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Chemical Thermodynamics and Molecular Structure"
    ]
  ],
  "openalex": "W7220393728",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15006218/v2",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-05",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/1rk2tbfwgyezt.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15006218",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15006218/v2"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Chemical Thermodynamics and Molecular Structure",
      "subfield": "organic"
    }
  ],
  "title": "Features of the Gibbs Equation (∆G = ∆H - T∆S) Applied to Solvation, Vaporization, and Complexation Thermodynamics",
  "title_text": "Features of the Gibbs Equation (∆G = ∆H - T∆S) Applied to Solvation, Vaporization, and Complexation Thermodynamics",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/1rk2tbfwgyezt",
  "venue": "ChemRxiv",
  "versions": []
}