Knudsen Effusion Mass Spectrometric Determination of Metal Hydroxide Stabilities

Gorokhov, L. N.; Milushin, M.I.; Emel’yanov, A. M.

doi:10.1007/978-1-4612-0481-7_29

Cited by 9 publications

(14 citation statements)

References 6 publications

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“…The error bars are based on the convergence properties observed for approach I using the DEA asymptote, the magnitude of the basis set superposition error (see Computational Details), as well as an uncertainty of 0.03 eV in the estimate of relativistic effects. The value for chromium hydroxide agrees well with the most recent experimental estimate, by Gorokhov et al at 3.86 ± 0.15 eV. When our computed value of IP(CrOH) at 7.54 ± 0.05 eV is combined with experimental values of the bond dissociation energy in the chromium hydroxide cation, two further experimental estimates of D 0 (Cr−OH) are obtained as 3.95 ± 0.23 and 4.00 ± 0.14 eV.…”

Section: Resultssupporting

confidence: 90%

Accurate Enthalpies of Formation for CrX(g), X = O, OH, and F. A Computational Study

Espelid¹,

Børve²

1997

J. Phys. Chem. A

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CrOH(g) is studied for the first time by theory, using accurate configuration interaction (CI) methods in conjunction with large basis sets. The ground and lowest excited state are established for the neutral and singly ionized molecule. The ionization potential is computed to 7.54 ± 0.05 eV, which, when applied to experimental results for CrOH+ [Magnera, T. F.; David, D. E.; Michl, J. J. Am. Chem. Soc. 1989, 111, 4100. Kang, H.; Beauchamp, J. L. J. Am. Chem. Soc. 1986, 108, 7502] opens access to experimental data on the bond dissociation energy in Cr−OH. Accurate quantum chemical methods have been applied to the calculation of bond dissociation energies of gaseous CrOH, CrF, and CrO. For the singly bound molecules the values obtained, D 0(Cr−OH) = 3.74 ± 0.10 eV and D 0(CrF) = 5.04 ± 0.10 eV, constitute the most accurate thermodynamical data available for these compounds. The high accuracy has been realized through the use of a dissociation process which is analogous to electron-attachment induced dissociation, leading to a high degree of cancelation of errors in the calculation of bond strengths in polar systems. In chromium monoxide, higher-than-triply excited configurations are important in the CI expansion, and an extrapolation procedure is applied to take these effects into account. The resulting estimate, D 0(CrO) = 4.69 ± 0.10 eV, confirms the experimental finding of Kang and Beauchamp [Kang, H.; Beauchamp, J. L. J. Am. Chem. Soc. 1986, 108, 5663]. Enthalpies of formation are calculated for the title molecules based on the computed bond dissociation energies.

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Section: Resultssupporting

confidence: 90%

Accurate Enthalpies of Formation for CrX(g), X = O, OH, and F. A Computational Study

Espelid¹,

Børve²

1997

J. Phys. Chem. A

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“…Note that if our preliminary value of 3.79 ± 0.12 eV is lowered by the Fe + ( 4 F) excitation energy of 0.30 eV, the resulting value is in good agreement with this recommendation. Further, Schröder and Schwarz [63] cite several other experimental values, including 3.17 ± 0.13 eV [65], 3.3 ± 0.2 eV [65], 3.34 ± 0.26 eV [66], and 3.9 ± 0.3 eV [67]. None of these seems particularly definitive, but the latter three values are all within the combined experimental error of 3.57 ± 0.14 eV.…”

Section: Appendix a Implications For The Bond Energy Of Feoh +mentioning

confidence: 88%

Ammonia activation by iron: state-specific reactions of Fe+(6D, 4F) with ND3 and the reaction of FeNH+ with D2

Liyanage

Armentrout

2005

International Journal of Mass Spectrometry

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“…These observations confirm the results of other authors who have predicted the presence of some of these species by thermodynamic calculations. [19][20][21][22][23] Under these conditions of oxidation no evidence was found of the presence of CrO 2 OH(g) and CrO 2 (OH) 2 (g), which had been reported by other authors as the dominant oxyhydroxide vapor species. [8][9][10] The result of the thermogravimetric study of this sample of Cr in Ar + 80% H 2 O at 650°C is shown in Fig.…”

Section: Methodsmentioning

confidence: 81%

Study by Means of the Mass Spectrometry of Volatile Species in the Oxidation of Cr, Cr2O3, Al, Al2O3, Si, SiO2, Fe and Ferritic/Martensitic Steel Samples at 923 K in Ar+(10 to 80%)H2O Vapor Atmosphere for New-Materials Design

Pérez-Trujillo

Castañeda

2006

Oxid Met

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and ferritic/martensitic steels (P91 and P92) at high temperatures. All samples were heated to 650°C at 1 atm in a mixture of Ar with 10-80% range H 2 O vapor. Oxidation times varied between 100 and 200 h. Cr(g), CrH(g), CrO(g), CrOH(g), CrO 2 (g), CrOOH(g) and Cr(OH) 2 (g) chromium-oxy-hydroxides species were identified during the corrosion of Cr oxidized in a steam atmosphere of Ar+80%H 2 O for 100 h. CrO(g), CrO 3 (g) and Cr(OH) 6 (g) species were present in mass loss of a Cr 2 O 3 sample in similar conditions for 200 h of oxidation. However a mass gain was observed when Cr 2 O 2 (g) and CrO(OH) 4 (g) species were present. Simultaneously, thermogravimetric studies of the oxidation kinetics of the samples were made with one in-situ thermobalance. The P91 and P92 steels were studied with afore-mentioned techniques at the beginning of breakaway oxidation. During 100 h of oxidation at 650°C in Ar+10%H 2 O atmosphere: Cr(OH) 6 (g), CrOOH(g) and CrO 2 (OH) 2 (g) chromium oxy-hydroxides volatile species were detected in the P91 steel, and Cr(OH) 2 (g), Cr(OH) 3 (g), Cr(OH) 4 (g), CrO(OH) 2 (g) 231 and CrO(OH) 4 (g), species in the P92 steel. The morphology/composition and structure of the oxidized steel samples were also characterized using SEM/ EDAX and XRD techniques, respectively.

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Knudsen Effusion Mass Spectrometric Determination of Metal Hydroxide Stabilities

Cited by 9 publications

References 6 publications

Accurate Enthalpies of Formation for CrX(g), X = O, OH, and F. A Computational Study

Accurate Enthalpies of Formation for CrX(g), X = O, OH, and F. A Computational Study

Ammonia activation by iron: state-specific reactions of Fe+(6D, 4F) with ND3 and the reaction of FeNH+ with D2

Study by Means of the Mass Spectrometry of Volatile Species in the Oxidation of Cr, Cr2O3, Al, Al2O3, Si, SiO2, Fe and Ferritic/Martensitic Steel Samples at 923 K in Ar+(10 to 80%)H2O Vapor Atmosphere for New-Materials Design

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