Abstract
AbstractIt is demonstrated that for the system perylene in butyronitril, the dimerization equilibria of radical cations R+ + R ⇌ R+2 (I) and 2R+ ⇌ R++2 (II), occur simultaneously. In order to determine thermodynamic data, the complex system can be divided in simple subsystems by employing the property that one component, the radical cations, is generated electrolytically. Thus from the derivative of the absorbance A with respect to the charge q consumed at q = 0, (dA/dq)q=0, the parameters of equilibrium I are obtained: −ΔH+ = (36 ± 6) kJ/mol, −ΔS+ = 71 ± 8) J/mol · K. The temperature variation of a nearly totally electrolyzed solution enables the determination of the parameters of equilibrium II: −ΔH++ = (45 ± 2) kJ/mol, −ΔS++ = (76 ± 8) J/mol · K. For equilibrium I the influence of the follow‐up reaction of perylene radical cations with traces of water could be described quantitatively (pseudo first‐order rate constant −2 · 10−3 s−1).
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callMore From: Berichte der Bunsengesellschaft für physikalische Chemie
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
