Energetics of electrode reactions. II. The relationship between redox potentials, ionization potentials, electron affinities, and solvation energies of aromatic hydrocarbons

1976 ◽  
Vol 98 (1) ◽  
pp. 98-103 ◽  
Author(s):  
Vernon D. Parker
Keyword(s):  
Aromatic Hydrocarbons ◽  
Ionization Potentials ◽  
Redox Potentials ◽  
Electron Affinities ◽  
Electrode Reactions ◽  
Solvation Energies ◽  
The Relationship

Electron affinities and Marcus reorganization energies. A correlation between gas phase electron affinities and solution phase redox potentials

1989 ◽  
Vol 67 (1) ◽  
pp. 171-175 ◽  
Author(s):  
Dennis D. Tanner ◽  
Natasha Deonarian ◽  
Abdelmajid Kharrat
Keyword(s):  
Cyclic Voltammetry ◽  
Aromatic Hydrocarbons ◽  
Solvation Energy ◽  
Polynuclear Aromatic Hydrocarbons ◽  
Redox Potentials ◽  
Electron Affinities ◽  
Solvation Energies ◽  
Linear Plot ◽  
Reorganization Energies ◽  
Linear Correlations

Redox potentials determined by cyclic voltammetry were used in conjunction with published electron affinities to determine the solvation energies for series of three classes of compounds: substituted benzoquinones, substituted nitrobenzenes, and polynuclear aromatic hydrocarbons. Excellent linear correlations were obtained between the measured electron affinities and the E0 of the substrates. The calculated electron affinities, EA (E0), were computed using the average solvation energies for the three classes of compounds, and were found to be in excellent agreement with the measured values. The nitrobenzenes and quinones had one solvation energy, while the aromatic hydrocarbons were correlated with a significantly different value. The solvation energy of a variety of compounds could also be related to their Marcus reorganization energiesλ(0), by a linear plot with a high correlation coefficient. From simple electrochemical measurements of similar compounds, either electron affinities or Marcus λ(0) values can be estimated. Keywords: electron affinities, Marcus reorganization energies, cyclic voltammetry.

scholarly journals Prediction of physico-chemical properties for polycyclic aromatic hydrocarbons based on electronic characteristics of molecules

2019 ◽  
Vol 59 (7) ◽  
pp. 116-121
Author(s):  
Mikhail Yu. Dolomatov ◽  
◽  
Natalia H. Paymurzina ◽  
Ella A. Kovaleva ◽  
◽  
...  
Keyword(s):  
Aromatic Hydrocarbons ◽  
Quantum Chemical ◽  
Chemical Properties ◽  
Ionization Potentials ◽  
Physical And Chemical Properties ◽  
Electron Affinities ◽  
Boiling Points ◽  
Polycyclic Aromatic ◽  
Physical And Chemical ◽  
And Chemical Properties

QSPR models have been developed to predict of polycyclic aromatic hydrocarbons (PAHs) based on quantum chemical and integral spectroscopic descriptors. The first ionization potentials calculated from the energies of the highest occupied molecular orbital (HOMO), relative autocorrelation empirical parameters and the total number of electrons of non-ionized molecules were used as quantum chemical descriptors. Ionization potentials, electron affinities, boiling points, molecular masses, saturation vapor pressure of PAHs were studied as physical-chemical properties. Ionization potentials and electron affinities (IPs and EAs) are calculated by the use of density functional theory (DFT). Relative empirical autocorrelation parameters µ were calculated from the spectra of PAH molecules experimentally obtained and taken from the databases. The predictive power of resulting model is demonstrated by testing it on unseen data that were not used during model generation. Coefficients of determination for all dependencies considered in this paper are not less than 0.95. To assess the reliability for coefficients of determination, their mean errors were calculated. In this paper, we compared theoretical (experimental) and model-calculated values. Relative errors were estimated: for the electron donating ability of PAHs is 1.11% (for IP) and 0.86% (for EA); at about 3.1% for boiling points; not more than 0.51% for molar mass, for saturated vapor pressure, the error is more significant, which is apparently due to the difficulties of determining this value. The obtained models make it possible to estimate physical and chemical properties with sufficient accuracy for practical applications. The research results can be practically used in petrochemistry, carbon chemistry, organic chemistry, for prediction of physical and chemical properties PAH molecules.

Electron affinities of aza-substituted polycyclic aromatic hydrocarbons

1989 ◽  
Vol 67 (10) ◽  
pp. 1628-1631 ◽  
Author(s):  
Glen W. Dillow ◽  
P. Kebarle
Keyword(s):  
Electron Transfer ◽  
Gas Phase ◽  
Aromatic Hydrocarbons ◽  
Radical Anions ◽  
Electron Affinities ◽  
Reduction Potentials ◽  
Dilute Gas ◽  
Solvation Energies ◽  
Polycyclic Aromatic ◽  
Electron Reduction

Electron affinities for aza-substituted polycyclic aromatics were determined from measurements of electron transfer equilibria in the dilute gas phase with a pulsed electron high pressure mass spectrometer (PHPMS). These are (in kcal/mol): quinazoline (12.7), quinoxaline (15.8), cinnoline (16.0), acridine (20.3), benzo[c]cinnoline (20.6), pyrido[2,3-b]pyrazine (22.5), phenazine (29.5). Solvation energies of the corresponding radical anions in acetonitrile and dimethylformamide are derived from the gas phase data and literature on electron reduction potentials in solution. An observed linear relationship between the electron affinities and the reduction potentials allows estimates of electron affinities to be made for 12 aza compounds whose EA's are too low to be measured with the present method. Keywords: aza-substituted aromatic hydrocarbons, electron affinities, electron transfer, radical anions, reduction potentials, solvation energies of radical anions, stabilities of radical anions.

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