Estimation des enthalpies de vaporisation des composes organiques liquides, partie 3. Application aux hydrocarbures insatures

Ducros, M.; Sannier, H.

doi:10.1016/0040-6031(82)85074-0

Cited by 19 publications

(7 citation statements)

References 4 publications

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“…In their next paper, Ducros et al extended the method to metalorganic compounds. 40 Here, deviations are much larger.…”

Section: Use Of Liquid-phase Data To Obtain Gas-phase Enthalpiesmentioning

confidence: 87%

“…In a series of papers which appear to have been long neglected, Ducros et a/. [38][39][40][41] have shown that group additivity can be applied to a series of compounds to estimate AVH°298> whence it is possible to estimate AfH°(g). For hydrocarbons, average deviations are the order of 0.1 kcal/mol.37'39 For alcohols, which would be expected to provide a severe test because of their structural hydrogen bonding, average deviations are about 0.2 kcal/mol.38 For the halides, nitriles, and other monofunctionalized organics, the authors chose an algebraic formula to represent the effect of chain length on primary-, secondary-, and tertiary-substituted carbons.…”

Section: Use Of Liquid-phase Data To Obtain Gas-phase Enthalpiesmentioning

confidence: 99%

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Estimation of heats of formation of organic compounds by additivity methods

Cohen¹,

Benson²

1993

Chem. Rev.

575

484

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“…In their next paper, Ducros et al extended the method to metalorganic compounds. 40 Here, deviations are much larger.…”

Section: Use Of Liquid-phase Data To Obtain Gas-phase Enthalpiesmentioning

confidence: 87%

Section: Use Of Liquid-phase Data To Obtain Gas-phase Enthalpiesmentioning

confidence: 99%

Estimation of heats of formation of organic compounds by additivity methods

Cohen¹,

Benson²

1993

Chem. Rev.

575

484

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“…65 Higher-order models for these properties have been proposed by Benson, 51 Constantinou and Gani, 52 Marrero and Gani. 53 Kolska et al, 66 developed higher-order GC-models for enthalpies of vaporization and entropies of vaporization at 298 K as well as at the normal boiling point of the compound and compared their models with other GC-models [67][68][69][70][71] for the same properties. All these models can be represented by eqn (7), although the groups sets for each model are different.…”

Section: 21mentioning

confidence: 99%

The calculation of thermodynamic properties of molecules

2010

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Thermodynamic data are key in the understanding and design of chemical processes. Next to the experimental evaluation of such data, computational methods are valuable and sometimes indispensable tools in obtaining heats of formation and Gibbs free energies. The major toolboxes to obtain such quantities by computation are quantum mechanical methods and group contribution methods. Although a lot of progress was made over the last decade, for the majority of chemical species we are still quite a bit away from what is often referred to as chemical accuracy, i.e.'1 kcal mol(-1)'. Currently, for larger molecules the combination of group contribution methods with group additive values that are determined with the best available computational ab initio methods seems to be a viable alternative to obtain thermodynamic properties near chemical accuracy. New developments and full use of existing tools may lead to further improvements (critical review, 83 references).

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“…Table contains some of the group additivity values of Ducros et al − for estimating Δ vap H °(298) for the compound in Table together with the modified values selected by the author and used here.…”

Section: Heat Of Formation and Entropy Of Liquids At Their Boiling Po...mentioning

confidence: 99%

“…Group additivity provides great facility in estimating the thermochemistry of gas-phase reactions for species whose thermochemistry has not been measured. , To have equal facility in dealing with the much larger realm of condensed phase reactions it is important to have methods for evaluating the relevant thermochemistry of species in the liquid state. A major step in this direction was taken by Ducros and co-workers − who showed that group additivity could be used to estimate heats of vaporization of organic and metal organic compounds at 298 K with good precision. This made possible the evaluation of Δ f H ° 298 ( l ) for those compounds for which gas-phase group values were available.…”

Section: Introductionmentioning

confidence: 99%

New Methods for Estimating the Heats of Formation, Heat Capacities, and Entropies of Liquids and Gases

Benson

1999

J. Phys. Chem. A

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Using group additivity values to estimate Δvap H°(298) and the Kistiakowsky equation to estimate both Δvap S°(T b) and Δvap H°(T b) at the boiling point (T b), it is shown how an average value of Δvap C p° can be obtained which can then be used to calculate values of Δvap S°(298). This latter can then be used in conjunction with S°(g,298) to calculate S°(l,298). Alternatively, where values of S°(l,298) are available but not S°(g,298) the latter can be calculated. The method applies to regular liquids, even those with relatively large dipoles but not to H-bonded liquids. The accuracy of estimated values of S°(l,298) are 0.45 ± 0.16 cal/(mol K) with a maximum deviation of 1.0 cal/(mol K) for an assortment of 14 selected compounds and 0.3 ± 0.12 for another 17 liquids for which groups are not available but Δvap H°(298) and Δvap S°(298) are. Here the largest deviation is 1.9 cal/(mol K). Calculated values of C p°(l,298) are much less accurate, ±3 cal/(mol K) with a maximum deviation of 9.0 cal/(mol K). It is also shown that the best average value of C p° to use in calculating changes in ΔH° and ΔS° in a specified temperature interval, T 1 to T 2, is the arithmetic mean of the initial and final values, [C p°(T 1) + C p°(T 2)]/2. Changes are recommended in some of the group values for calculating Δvap H°(298) and also in the group O−(C)2 for calculating gas-phase entropies of ethers and for N−(C)2(H) for calculating entropies of secondary amines.

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Estimation des enthalpies de vaporisation des composes organiques liquides, partie 3. Application aux hydrocarbures insatures

Cited by 19 publications

References 4 publications

Estimation of heats of formation of organic compounds by additivity methods

Estimation of heats of formation of organic compounds by additivity methods

The calculation of thermodynamic properties of molecules

New Methods for Estimating the Heats of Formation, Heat Capacities, and Entropies of Liquids and Gases

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