Entropy considerations in kinetic method experiments

Journal of Mass Spectrometry : JMS
C Wesdemiotis

Abstract

In extended kinetic method experiments, relative binding enthalpies ('affinities') and relative entropies are obtained based on unimolecular dissociation kinetics. A series of ion-bound dimers A-X-B(i) is formed, in which the sample (A) and structurally similar reference molecules (B(i)) are bridged by a central cation or anion (X). The branching ratios of the A-X-B(i) set to A-X and B(i)-X are determined at different internal energies, usually by subjecting A-X-B(i) to collisionally activated dissociation at various collision energies. The dependence of the natural logarithm of the branching ratios on the corresponding B(i)-X bond enthalpies (X affinities of B(i)) is evaluated as a function of internal energy to thereby deduce the A-X bond enthalpy (X affinity of A) as well as an apparent relative entropy of the competitive dissociation channels, Delta(DeltaS(app)). Experiments with proton- and Na(+)-bound dimers show that this approach can yield accurate binding enthalpies. In contrast, the derived Delta(DeltaS(app)) values do not correlate with the corresponding thermodynamic entropy differences between the channels leading to A-X and B(i)-X, even after scaling. The observed trends are reconciled by the transition state swit...Continue Reading

Citations

Jun 1, 2005·Journal of the American Society for Mass Spectrometry·Joshua J WindJohn C Poutsma
Jul 11, 2006·Journal of the American Society for Mass Spectrometry·Christian BleiholderBéla Paizs
Oct 28, 2006·Journal of the American Society for Mass Spectrometry·John P Tan, Jianhua Ren
Dec 13, 2006·Journal of the American Society for Mass Spectrometry·Ping WangGilles Ohanessian
Sep 16, 2008·Journal of the American Society for Mass Spectrometry·Francoise FournierJean-Claude Tabet
Nov 7, 2009·Journal of the American Society for Mass Spectrometry·Sangeeta KumariMariappanadar Vairamani
Nov 13, 2007·Journal of Mass Spectrometry : JMS·Ping WangChrys Wesdemiotis
Sep 15, 2007·Mass Spectrometry Reviews·Guy Bouchoux
Jul 11, 2006·Journal of Mass Spectrometry : JMS·Guy Bouchoux
Nov 14, 2012·Journal of Mass Spectrometry : JMS·Andreina RicciPierluigi Giacomello
Jan 6, 2016·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Kacper BłaziakWitold Danikiewicz
Jul 28, 2016·The Journal of Physical Chemistry. B·Patrick Batoon, Jianhua Ren
Aug 21, 2010·Journal of the American Chemical Society·Lucie DuchácckováJana Roithová
Mar 19, 2005·European Journal of Mass Spectrometry·Guy BouchouxMichel Sablier
Nov 9, 2004·Journal of Mass Spectrometry : JMS
May 19, 2006·The Journal of Physical Chemistry. a·Olivia E SchroederJohn C Poutsma
Oct 6, 2006·The Journal of Physical Chemistry. a·Erica J AndrioleJohn C Poutsma
Nov 1, 2008·The Journal of Organic Chemistry·Min LiuJeehiun K Lee
Sep 17, 2009·The Journal of Physical Chemistry. a·Jianhua RenRobert T Harper
May 8, 2020·The Journal of Physical Chemistry. a·Charly MayeuxLionel Massi
Sep 27, 2007·The Journal of Physical Chemistry. a·Isabelle Compagnon, Philippe Dugourd

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