TITLE

First principles electrochemistry: Electrons and protons reacting as independent ions

AUTHOR(S)
Llano, Jorge; Eriksson, Leif A.
PUB. DATE
December 2002
SOURCE
Journal of Chemical Physics;12/8/2002, Vol. 117 Issue 22, p10193
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
We here present a first principles approach to calculate standard Gibbs energies and the corresponding observables (standard electrode potentials in the hydrogen scale E[SUP0,SUBSHE] and pK[SUBa] values) of stoichiometric reactions involving electrons and/or protons as independent species in solution, from absolute electrochemical potentials defined according to quantum and statistical mechanics. In order to pass from the conventional electrodic and thermodynamic descriptions of electrochemistry to the first principles approach based on estimating absolute electrochemical potentials, we revisit the problem of the absolute and relative electrochemical scales from the macroscopic and microscopic viewpoints. A microscopic definition of the absolute electrochemical potential is presented in order to enable an identical thermodynamic treatment of any species in a given phase, i.e., electrons, protons, atoms, molecules, atomic and molecular ions, and electronically excited species. We show that absolute standard chemical potentials in the mole fraction scale can be easily computed with wave function and density functional theories in conjunction with self-consistent reaction field models. Based on Boltzmann and Fermi-Dirac statistics and experimental solvation data, we estimate an internally compatible set of absolute standard chemical and electrochemical potentials of protons and solvated electrons in the molality and molarity scales in aqueous solution at 298 K and 1 atm, within an absolute error of ± 0.5 kcal/mol. This scheme enables a consistent and simultaneous description of the Gibbs energy changes and the observables (E[SUP0,SUBSHE] and pK[SUBa']s) of electron, proton, and proton-coupled electron transfer reactions in aqueous solution at 298 K and 1 atm.
ACCESSION #
8528020

 

Related Articles

  • SQUARE-WAVE CATHODIC ADSORPTIVE STRIPPING VOLTAMMETRY OF RISPERIDONE. Tasdemir, Ibrahim Hüdai; Çakirer, Orhan; Erk, Nevin; Kiliç, Esma // Collection of Czechoslovak Chemical Communications;2011, Vol. 76 Issue 3, p159 

    Electrochemical properties and diffusion-adsorption behavior of risperidone (RPN), an antiphyscotic drug, on hanging mercury drop electrode (HMDE) were carried out in Britton- Robinson (BR) buffer. Some electrochemical parameters such as diffusion coefficient, number of transferred electrons and...

  • Embrittlement of austempered ductile iron on contact with water–testing under applied potential. Masud, L.; Martínez, R.; Simison, S.; Boeri, R. // Journal of Materials Science;Jul2003, Vol. 38 Issue 13, p2971 

    Recent reports indicate that austempered ductile iron (ADI) is embrittled on contact with water. This environmentally induced cracking (EIC) phenomenon is not clearly understood. The objective of this investigation is to study the behavior of ADI on tensile testing in aqueous media under...

  • MnO2 cathode in an aqueous Li2SO4 solution for battery applications. Minakshi, Manickam; Mitchell, David R. G. // Journal of Applied Electrochemistry;Jan2009, Vol. 39 Issue 1, p1 

    A manganese dioxide (MnO2) cathode with zinc (Zn) as the anode has been investigated using lithium sulphate (Li2SO4) as an electrolyte. Previously we demonstrated that cells comprising MnO2 and lithium hydroxide (LiOH) as an electrolyte can be made rechargeable to over one-electron capacity with...

  • Voltammetric Method Using Multi-Walled Carbon Nanotubes Modified Glassy Carbon Electrode for the Determination of Terbutaline Sulfate in Pork Sample. Wei Xu; Rulin Lei; Wenying Cao; Chunhui Guo; Xiuhua Zhang; Shengfu Wang // Journal of Analytical Sciences, Methods & Instrumentation;Jun2013, Vol. 3 Issue 2, p75 

    Electrochemical properties of terbutaline sulfate (TBS) at the glassy carbon electrode modified with multi-walled car-bon nanotubes (MWNTs) were explored by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The response was evaluated with respect to pH, scan rate and other...

  • Electrons. Farndon, John // Science (1-59084-471-8);2003, p11 

    Electrons are the smallest of the three main, stable parts of an atom, which also has protons and neutrons. Electrons are packets of energy that travel as waves, arrive as particles, and have a negative electrical charge. They cling to the nucleus because of the proton's positive charge. They...

  • Electron-density distribution in a laser tube with a hyperboloid of revolution boundary. Kanoussis, Demetrios P.; Demas, Nicholas G.; Ventrice, Carl A. // Journal of Applied Physics;2/15/1987, Vol. 61 Issue 4, p1317 

    Focuses on a study which determine the electron-density distribution in a laser tube formed by a hyperboloid of spherical end surfaces. Diffusion equations; Geometrical considerations; Computational procedure and assumptions.

  • A photoelectron spectroscopic study of the electrochemical processes in polyaniline. Snauwaert, P.; Lazzaroni, R.; Riga, J.; Verbist, J. J.; Gonbeau, D. // Journal of Chemical Physics;2/15/1990, Vol. 92 Issue 4, p2187 

    The electronic structure of the base forms of electrochemically prepared polyaniline is studied by means of x-ray photoelectron spectroscopy (XPS). Model compounds for the amine, imine and crosslinked nitrogen sites provide the references for the analysis of the core level spectra in the...

  • Temperature effect on the deactivation of electronically excited potassium by hydrogen molecule. Hsiao, Yen-Chin; Yen-Ching Hsiao; Liu, Dean-Kuo; Dean-Kuo Liu; Fung, Hok-Sum; Hok-Sum Fung; Lin, King-Chuen; King-Chuen Lin // Journal of Chemical Physics;9/15/2000, Vol. 113 Issue 11 

    Time-resolved fluorescences from varied K excited states are monitored as a function of H[sub 2] pressure. According to a three-level model, the rate coefficients of collisional deactivation for the K 6 [sup 2]S, 7 [sup 2]S, and 8 [sup 2]S states at 473 K have been determined to be 4.94±0.15,...

  • Results of a Residential Proton Exchange Membrane (PEM) Fuel Cell Demonstration at a Military Facility in New York. Holcomb, Franklin H.; Davenport, Brian C.; Josefik, Nicholas M.; Binder, Michael J. // ASHRAE Transactions;2004, Vol. 110 Issue 1, p25 

    Residential proton exchange membrane (PEM) fuel cells are in the precommercial stages of development, and limited field testing and demonstrations have been performed to date. This paper provides an overview of the Department of Defense (DOD) Residential PEM Fuel Cell Demonstration Program, as...

Share

Read the Article

Courtesy of THE LIBRARY OF VIRGINIA

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics