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Complex phosphorus thermochemistry. Volume-based thermodynamics and the estimation of standard enthalpies of formation of gas phase ions: Delta H-f degrees(PCl4+, g) and Delta H-f degrees(PCl6-, g)
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Jenkins, H. Donald Brooke (2008) Complex phosphorus thermochemistry. Volume-based thermodynamics and the estimation of standard enthalpies of formation of gas phase ions: Delta H-f degrees(PCl4+, g) and Delta H-f degrees(PCl6-, g). Inorganic Chemistry, Vol.47 (No.18). pp. 8420-8425. doi:10.1021/ic800990k ISSN 0020-1669.
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Official URL: http://dx.doi.org/10.1021/ic800990k
Abstract
Energy-resolved collision-induced dissociation in a flowing afterglow-guided ion beam tandem mass spectrometer has recently enabled the accurate determination of the standard enthalpy of formation of the gaseous phosphorus pentachloride cation, Delta H-f degrees([PCl4+], g), found to be 414 +/- 17 kJ mol(-1) (giving a value of 378 +/- 18 kJ mol(-1) at 0 K). Such experimental values for the standard enthalpy of formation of gas phase complex are now being incorporated into the NIST standard reference data program. Such results, can, inter alia, provide a benchmark by which to test earlier computationally based methods which were made to estimate such quantities in the absence of any experimental data. The establishment of this value experimentally also affords us with the opportunity to explore the likely success of newer, simpler approaches. Previous large-scale direct minimization computations to estimate this (and other) standard enthalpies of formation match very well these new experimental results. This paper raises the question as to whether the much simpler volume-based thermodynamics (VBT) approach could yield equally satisfactory results and so circumvent, completely, the need for detailed modeling of the lattices involved. The conclusion is that the VBT approach portrays the extremely complex thermodynamics quite adequately. Thus for the purposes of obtaining basic thermodynamic data, complex modeling of the underlying structures involved may no longer be necessary. At least this should be the case for highly symmetrical ions, like PCl4+, where detailed packing with counterions is possibly less important than in other cases and where covalent interactions (less easily modeled) with neighboring ions is unlikely to be strongly featured. Other gaseous complex ion enthalpies of formation are also predicted here.
| Item Type: | Journal Article | ||||
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| Subjects: | Q Science > QC Physics Q Science > QD Chemistry |
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| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Thermochemistry, Thermodynamics, Enthalpy, Ionized gases, Complex ions | ||||
| Journal or Publication Title: | Inorganic Chemistry | ||||
| Publisher: | American Chemical Society | ||||
| ISSN: | 0020-1669 | ||||
| Official Date: | 15 September 2008 | ||||
| Dates: |
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| Volume: | Vol.47 | ||||
| Number: | No.18 | ||||
| Number of Pages: | 6 | ||||
| Page Range: | pp. 8420-8425 | ||||
| DOI: | 10.1021/ic800990k | ||||
| Status: | Peer Reviewed | ||||
| Publication Status: | Published |
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