Computational study of the thermodynamic properties of organophosphorus(V) compounds

Дорофеева, О. В.; Ryzhova, Oxana N.; Zverev, Vasilii G.

doi:10.1016/j.theochem.2006.12.053

Cited by 12 publications

(25 citation statements)

References 15 publications

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“…The results in Table show that the W1X‐1 and CBS‐QB3 derived group pair contributions to enthalpy differ, on average, by 5 kJ mol −1 , in good agreement with the performance of the two methods in predicting the standard formation enthalpies of aryl‐substituted phosphines and phosphine oxides. The enthalpy values in Table can be compared with the G3X data published by Dorofeeva and Moiseeva (where available) . Enthalpy contributions of 53, 119, and −181 kJ mol −1 have been reported for groups P‐(H 2 )(C B ), P‐(C B ) 3 , and PO‐(C B ) 3 , respectively, which, together with the contribution of 3 kJ mol −1 for the groups C B ‐(C B ) 2 (P) and C B ‐(C B ) 2 (PO), lead to the G3X values listed in Table .…”

Section: Resultsmentioning

confidence: 84%

“…Table reports W1X‐1 and CBS‐QB3 thermochemical data for the 19 alkyl and aryl phosphines considered in this work; CBS‐QB3 entropies and heat capacities have been omitted as they are nearly identical with the W1X‐1 data. Experimental values and G3X results reported by Dorofeeva and Moiseeva have been included in Table for comparison purposes (where available) …”

Section: Resultsmentioning

confidence: 99%

“…W1X-1 CBS-QB3 G3X [37][38][39] Exptl. [72][73][74][75][76] W1X-1 W1X- been included in Table 1 for comparison purposes (where available).…”

Section: W1x-1 and Cbs-qb3 Thermochemical Datamentioning

confidence: 99%

See 2 more Smart Citations

Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species

et al. 2018

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Composite quantum chemical methods W1X‐1 and CBS‐QB3 are used to calculate the gas phase standard enthalpy of formation, entropy, and heat capacity of 38 phosphines and phosphine oxides for which reliable experimental thermochemical information is limited or simply nonexistent. For alkyl phosphines and phosphine oxides, the W1X‐1, and CBS‐QB3 results are mutually consistent and in excellent agreement with available G3X values and empirical data. In the case of aryl‐substituted species, different computational methods show more variation, with G3X enthalpies being furthest from experimental values. The calculated thermochemical data are subsequently used to determine Benson group additivity contributions for 24 Benson groups and group pairs involving phosphorus, thereby allowing fast and accurate estimations of thermochemical data of many organophosphorus compounds of any complexity. Such data are indispensable, for example, in chemical process design or estimating potential hazards of new chemical compounds. © 2018 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 84%

Section: Resultsmentioning

confidence: 99%

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Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species

et al. 2018

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“…These compounds can also be used as efficient coke-reducing additives within thermal cracking processes [4,5]. However, experimental thermochemical and kinetic data are either unavailable or available but with relatively large uncertainties [6,7]. To remedy this problem, the calculation of these quantities through current techniques of computational quantum chemistry or with empirical rules is needed.…”

Section: Introductionmentioning

confidence: 99%

A simple way to predict vibrational zero point energy of organophosphorus (III) compounds

Rahal

Bouabdallah

Malek

et al. 2015

Computational and Theoretical Chemistry

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“…In 2000, in the aim of investigating the thermal degradation of chemical warfare surrogates, Glaude et al 23 reported thermochemical data obtained with PM3 semiempirical calculations 24 27 Thermochemical properties (enthalpy, entropy, and heat capacity) of 40 compounds containing pentavalent P atoms were evaluated at the same level of theory using the atomization energy procedure and an explicit treatment of the hindered rotors. 28 More recently, high accuracy theoretical calculations based on coupled cluster theory were implemented for the determination of enthalpy of formation of few phosphorus compounds, but only for species containing a limited number of heavy atoms. 29,30 Zhu and Bozzelli 31,32 used several density functional and ab initio computational methods to determine thermochemical parameters, reaction paths, and kinetic barriers for sulfur compounds.…”

Section: ■ Introductionmentioning

confidence: 99%

Quantum Chemical Study of the Thermochemical Properties of Organophosphorous Compounds

et al. 2015

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Organophosphorous compounds are involved in many toxic compounds such as fungicides, pesticides, or chemical warfare nerve agents. The understanding of the decomposition chemistry of these compounds in the environment is largely limited by the scarcity of thermochemical data. Because of the high toxicity of many of these molecules, experimental determination of their thermochemical properties is very difficult. In this work, standard gas-phase thermodynamic data, i.e., enthalpies of formation (ΔfH298°), standard entropies (S298°), and heat capacities (Cp°(T)), were determined using quantum chemical calculations and more specifically the CBS-QB3 composite method, which was found to be the best compromise between precision and calculation time among high accuracy composite methods. A large number of molecules was theoretically investigated, involving trivalent and pentavalent phosphorus atoms, and C, H, O, N, S, and F atoms. These data were used to propose 83 original groups, used in the semiempirical group contribution method proposed by Benson. Thanks to these latter group values, thermochemical properties of several nerve agents, common pesticides and herbicides have been evaluated. Bond dissociations energies (BDE), useful for the analysis the thermal stability of the compounds, were also determined in several molecules of interest.

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Computational study of the thermodynamic properties of organophosphorus(V) compounds

Cited by 12 publications

References 15 publications

Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species

Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species

A simple way to predict vibrational zero point energy of organophosphorus (III) compounds

Quantum Chemical Study of the Thermochemical Properties of Organophosphorous Compounds

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