The Relationship Between Molecular Symmetry and Physicochemical Properties Involving Boiling and Melting of Organic Compounds

David Humberto Lopez, Samuel Hyman Yalkowsky

Research output: Contribution to journalArticlepeer-review

Abstract

Objective and Methods: The reliable estimation of phase transition physicochemical properties such as boiling and melting points can be valuable when designing compounds with desired physicochemical properties. This study explores the role of external rotational symmetry in determining boiling and melting points of select organic compounds. Using experimental data from the literature, the entropies of boiling and fusion were obtained for 541 compounds. The statistical significance of external rotational symmetry number on entropies of phase change was determined by using multiple linear regression. In addition, a series of aliphatic hydrocarbons, polysubstituted benzenes, and di-substituted napthalenes are used as examples to demonstrate the role of external symmetry on transition temperature. Results: The results reveal that symmetry is not well correlated with boiling point but is statistically significant in melting point. Conclusion: The lack of correlation between the boiling point and the symmetry number reflects the fact that molecules have a high degree of rotational freedom in both the liquid and the vapor. On the other hand, the strong relationship between symmetry and melting point reflects the fact that molecules are rotationally restricted in the crystal but not in the liquid. Since the symmetry number is equal to the number of ways that the molecule can be properly oriented for incorporation into the crystal lattice, it is a significant determinant of the melting point.

Original languageEnglish (US)
Pages (from-to)2801-2815
Number of pages15
JournalPharmaceutical Research
Volume40
Issue number12
DOIs
StatePublished - Dec 2023

Keywords

  • boiling point
  • entropy of boiling
  • entropy of melting
  • hydrogen bonding
  • melting point
  • rotational symmetry

ASJC Scopus subject areas

  • Biotechnology
  • Molecular Medicine
  • Pharmacology
  • Pharmaceutical Science
  • Organic Chemistry
  • Pharmacology (medical)

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