The Relative Thermodynamic Stability of Diamond and Graphite

• Published in: Angewandte Chemie International Edition Vol. 60; no. 3; pp. 1546 - 1549
• Main Authors: White, Mary Anne, Kahwaji, Samer, Freitas, Vera L. S., Siewert, Riko, Weatherby, Joseph A., Ribeiro da Silva, Maria D. M. C., Verevkin, Sergey P., Johnson, Erin R., Zwanziger, Josef W.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 18.01.2021
• Edition: International ed. in English
• Subjects: density-functional calculations; diamond; Diamonds; Entropy; Graphite; Low temperature; Mathematical analysis; phase stability; Pressure; Stability; thermodynamics; density-functional calculations; thermodynamics; diamond; graphite; phase stability
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202009897

Recent density‐functional theory (DFT) calculations raised the possibility that diamond could be degenerate with graphite at very low temperatures. Through high‐accuracy calorimetric experiments closing gaps in available data, we reinvestigate the relative thermodynamic stability of diamond and graphite. For T<400 K, graphite is always more stable than diamond at ambient pressure. At low temperatures, the stability is enthalpically driven, and entropy terms add to the stability at higher temperatures. We also carried out DFT calculations: B86bPBE‐25X‐XDM//B86bPBE‐XDM and PBE0‐XDM//PBE‐XDM results overlap with the experimental −TΔS results and bracket the experimental values of ΔH and ΔG, displaced by only about 2× the experimental uncertainty. Revised values of the standard thermodynamic functions for diamond are ΔfHo=−2150±150 J mol−1, ΔfSo=3.44±0.03 J K−1 mol−1 and ΔfGo=−3170±150 J mol−1. Through experimental thermodynamics and density‐functional theory, it is shown that graphite is more stable than diamond for T<400 K.