Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Experiment Videos

Self-assembly does not account for the hydrophobic effect.

Michael H Abraham1, Michael J Blandamer

  • 1Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, U.K. m.h.abraham@ucl.ac.uk

Journal of the American Chemical Society
|June 27, 2002
PubMed
Summary

Thermodynamic analysis of non-electrolyte activity coefficients is corrected by accounting for molecular interactions. This study refutes the need for self-assembly to explain high activity coefficients in solutions.

Related Concept Videos

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

Descriptors for some compounds with pharmacological activity; calculation of properties.

International journal of pharmaceutics·2022
Same author

Group Contribution and Machine Learning Approaches to Predict Abraham Solute Parameters, Solvation Free Energy, and Solvation Enthalpy.

Journal of chemical information and modeling·2022
Same author

Properties of the tert-butyl halide solvolysis transition states.

Physical chemistry chemical physics : PCCP·2021
Same author

Linear free energy relationship models for the retention of partially ionized acid-base compounds in reversed-phase liquid chromatography.

Journal of chromatography. A·2020
Same author

Comments on "Classification of biphasic solvent systems according to Abraham descriptors for countercurrent chromatography".

Journal of chromatography. A·2020
Same author

Characterization of hydrophilic interaction liquid chromatography retention by a linear free energy relationship. Comparison to reversed- and normal-phase retentions.

Analytica chimica acta·2019

Area of Science:

  • Physical Chemistry
  • Thermodynamics
  • Solution Chemistry

Background:

  • Marmur proposed that high activity coefficients for non-electrolytes, especially in hydrophobic interactions, challenge thermodynamic explanations.
  • Marmur suggested solute self-assembly as a solution to thermodynamic inconsistencies.

Purpose of the Study:

  • To demonstrate the incorrectness of Marmur's thermodynamic analysis.
  • To show that standard thermodynamics can explain high activity coefficients without invoking self-assembly.

Main Methods:

  • Re-evaluating Marmur's analysis by incorporating the equilibrium between monomeric and associated solute molecules.
  • Calculating activity coefficients using established molecule-molecule interaction models.

Main Results:

Related Experiment Videos

  • Marmur's analysis was found to be incorrect due to ignoring solute-solute equilibria.
  • Calculated activity coefficients for nitromethane in hexane (31.9) and hexane in water (4.71 x 10^5) align with experimental values.
  • The results validate thermodynamic models without requiring self-assembly assumptions.

Conclusions:

  • High non-electrolyte activity coefficients are explicable through established thermodynamic principles and molecule-molecule interactions.
  • The concept of solute self-assembly is unnecessary to resolve discrepancies in thermodynamic activity coefficient calculations.
  • Accurate thermodynamic modeling accounts for solute-solute equilibria, resolving apparent paradoxes.