Schröder Detlef
Institute of Organic Chemistry and Biochemistry, 16610 Prague 6, Czech Republic.
J Phys Chem A. 2008 Dec 18;112(50):13215-24. doi: 10.1021/jp8030804.
The experimental and theoretical thermochemistry of the gaseous neutral and ionic iron oxides and hydroxides FeO, FeOH, FeO(2), OFeOH, and Fe(OH)(2) and of the related cationic water complexes Fe(H(2)O)(+), (H(2)O)FeOH(+), and Fe(H(2)O)(2)(+) is analyzed comprehensively. A combination of data for the neutral species with those of the gaseous ions in conjunction with some additional measurements provides a refined and internally consistent compilation of thermochemical data for the neutral and ionic species. In terms of heats of formation at 0 K, the best estimates for the gaseous, mononuclear FeO(m)H(n)(-/0/+/2+) species with m = 1, 2 and n = 0-4 are Delta(f)H(FeO(-)) = (108 +/- 6) kJ/mol, Delta(f)H(FeO) = (252 +/- 6) kJ/mol, Delta(f)H(FeO(+)) = (1088 +/- 6) kJ/mol, Delta(f)H(FeOH) = (129 +/- 15) kJ/mol, Delta(f)H(FeOH(+)) = (870 +/- 15) kJ/mol, Delta(f)H(FeO(2)(-)) = (-161 +/- 13) kJ/mol, Delta(f)H(FeO(2)) = (67 +/- 12) kJ/mol, Delta(f)H(FeO(2)(+)) = (1062 +/- 25) kJ/mol, Delta(f)H(OFeOH) = (-84 +/- 17) kJ/mol, Delta(f)H(OFeOH(+)) = (852 +/- 23) kJ/mol, Delta(f)H(Fe(OH)(2)(-)) = -431 kJ/mol, Delta(f)H(Fe(OH)(2)) = (-322 +/- 2) kJ/mol, and Delta(f)H(Fe(OH)(2)(+)) = (561 +/- 10) kJ/mol for the iron oxides and hydroxides as well as Delta(f)H(Fe(H(2)O)(+)) = (809 +/- 5) kJ/mol, Delta(f)H((H(2)O)FeOH(+)) = 405 kJ/mol, and Delta(f)H(Fe(H(2)O)(2)(+)) = (406 +/- 6) kJ/mol for the cationic water complexes. In addition, charge-stripping data for several of several-iron-containing cations are re-evaluated due to changes in the calibration scheme which lead to Delta(f)H(FeO(2+)) = (2795 +/- 28) kJ/mol, Delta(f)H(FeOH(2+)) = (2447 +/- 30) kJ/mol, Delta(f)H(Fe(H(2)O)(2+)) = (2129 +/- 29) kJ/mol, Delta(f)H((H(2)O)FeOH(2+)) = 1864 kJ/mol, and Delta(f)H(Fe(H(2)O)(2)(2+)) = (1570 +/- 29) kJ/mol, respectively. The present compilation thus provides an almost complete picture of the redox chemistry of mononuclear iron oxides and hydroxides in the gas phase, which serves as a foundation for further experimental studies and may be used as a benchmark database for theoretical studies.
全面分析了气态中性和离子态的氧化铁和氢氧化铁FeO、FeOH、FeO₂、OFeOH和Fe(OH)₂以及相关阳离子水络合物Fe(H₂O)⁺、(H₂O)FeOH⁺和Fe(H₂O)₂²⁺的实验和理论热化学。将中性物种的数据与气态离子的数据相结合，并结合一些额外的测量，得到了中性和离子物种热化学数据的精确且内部一致的汇编。就0K时的生成热而言，对于m = 1、2且n = 0 - 4的气态单核FeOₘHₙ⁻/⁰/⁺/²⁺物种，最佳估计值为：对于氧化铁和氢氧化铁，ΔfH(FeO⁻) = (108 ± 6) kJ/mol，ΔfH(FeO) = (252 ± 6) kJ/mol，ΔfH(FeO⁺) = (1088 ± 6) kJ/mol，ΔfH(FeOH) = (129 ± 15) kJ/mol，ΔfH(FeOH⁺) = (870 ± 15) kJ/mol，ΔfH(FeO₂⁻) = (-161 ± 13) kJ/mol，ΔfH(FeO₂) = (67 ± 12) kJ/mol，ΔfH(FeO₂⁺) = (1062 ± 25) kJ/mol，ΔfH(OFeOH) = (-84 ± 17) kJ/mol，ΔfH(OFeOH⁺) = (852 ± 23) kJ/mol，ΔfH(Fe(OH)₂⁻) = -431 kJ/mol，ΔfH(Fe(OH)₂) = (-322 ± 2) kJ/mol，ΔfH(Fe(OH)₂⁺) = (561 ± 10) kJ/mol；对于阳离子水络合物，ΔfH(Fe(H₂O)⁺) = (809 ± 5) kJ/mol，ΔfH((H₂O)FeOH⁺) = 405 kJ/mol，ΔfH(Fe(H₂O)₂²⁺) = (406 ± 6) kJ/mol。此外，由于校准方案的变化，重新评估了几种含铁阳离子的电荷剥离数据，得到ΔfH(FeO²⁺) = (2795 ± 28) kJ/mol，ΔfH(FeOH²⁺) = (2447 ± 30) kJ/mol，ΔfH(Fe(H₂O)₂⁺) = (2129 ± 29) kJ/mol，ΔfH((H₂O)FeOH²⁺) = 1864 kJ/mol，ΔfH(Fe(H₂O)₂²²⁺) = (1570 ± 29) kJ/mol。因此，本汇编几乎完整地呈现了气相中单核氧化铁和氢氧化铁的氧化还原化学，为进一步的实验研究奠定了基础，并可作为理论研究的基准数据库。
