Prediction of thermodynamic properties: centerpiece approach—how do we avoid confusion and get reliable results?

Verevkin, Sergey P.; Андреева, И. В.; Zherikova, Kseniya V.; Pimerzin, Aleksey A.

doi:10.1007/s10973-021-11115-4

Cited by 18 publications

(13 citation statements)

References 23 publications

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“…Using the same method for ionic liquids composed of large organic cations and large organic/inorganic anions is impractical, due to too many “bricks” and a very limited amount of available experimental enthalpies of vaporization. To overcome these limitations, we developed a general approach to estimate the vaporization enthalpies based on a so-called “centerpiece” molecule [ 40 , 41 ]. This approach is closely related to the broadly used group additivity (GA) methods [ 39 , 42 ].…”

Section: Resultsmentioning

confidence: 99%

Aprotic Ionic Liquids: A Framework for Predicting Vaporization Thermodynamics

2022

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Ionic liquids (ILs) are recognized as an environmentally friendly alternative to replacing volatile molecular solvents. Knowledge of vaporization thermodynamics is crucial for practical applications. The vaporization thermodynamics of five ionic liquids containing a pyridinium cation and the [NTf2] anion were studied using a quartz crystal microbalance. Vapor pressure-temperature dependences were used to derive the enthalpies of vaporization of these ionic liquids. Vaporization enthalpies of the pyridinium-based ionic liquids available in the literature were collected and uniformly adjusted to the reference temperature T = 298.15 K. The consistent sets of evaluated vaporization enthalpies were used to develop the “centerpiece”-based group-additivity method for predicting enthalpies of vaporization of ionic compounds. The general transferability of the contributions to the enthalpy of vaporization from the molecular liquids to the ionic liquids was established. A small, but not negligible correction term was supposed to reconcile the estimated results with the experiment. The corrected “centerpiece” approach was recommended to predict the vaporization enthalpies of ILs.

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Section: Resultsmentioning

confidence: 99%

Aprotic Ionic Liquids: A Framework for Predicting Vaporization Thermodynamics

2022

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“…Predicting properties using this idea in Tatevsky's original form is impractical. However, we have modified this idea and developed a "centerpiece" approach [28,29], in which the role of the "first-order" environment is played by a large molecule (see Fig. 3a) with welldefined experimental data.…”

Section: Fig 1 Visualization Of the First-order Group Additivity Tech...mentioning

confidence: 99%

Thermochemistry in the twenty-first century–quo vadis? In silico assisted diagnostics of available thermochemical data

Verevkin

Samarov

2022

Struct Chem

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Which comes first, experiment or theory? The answer is obvious—the experiment comes first. But how to be sure that the result of the experiment is reliable? Perhaps the crucial criterion is that the result should be consistent with the network of knowledge already available. In this study, we propose a step-by-step algorithm for quality diagnostics of thermochemical data on enthalpies of formation and enthalpies of phase transitions of organic compounds. The consistency of the data is studied and established using empirical structure–property correlations as well as using quantum chemical calculations. The diagnostic algorithm is exemplarily demonstrated on a series of alkyl-substituted benzophenones for which conflicting thermochemical data were available.

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“…The basic idea of the "centerpiece approach" approach is to select a relatively large "centerpiece molecule" (rather than the traditional summation of group contributions) with wellknown thermodynamic properties that structurally most closely resembles the molecule of interest [28,29]. Related to the compounds discussed in this paper, the benzophenone itself is the most suitable "centerpiece" molecule.…”

Section: Construction Of a Strain-free Theoretical Frameworkmentioning

confidence: 99%

“…Predicting properties using this idea in Tatevsky´s original form is impractical. However, we have modified this idea and developed a "centerpiece" approach [28,29],…”

Section: Introductionmentioning

confidence: 99%

Thermochemistry in 21 st century – Quo Vadis? In silico assisted diagnostics of available thermochemical data

Verevkin

Samarov

2022

Preprint

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Which comes first, experiment or theory? The answer is obvious – the experiment comes first. But how to be sure that the result of the experiment is reliable? Perhaps the crucial criterion is that the result should be consistent with the network of knowledge already available. In this study, we propose a step-by-step algorithm for quality diagnostics of thermochemical data on enthalpies of formation and enthalpies of phase transitions of organic compounds. The consistency of the data is studied and established using empirical structure-property correlations as well as using high-level quantum chemical calculations. The diagnostic algorithm is exemplarily demonstrated on a series of alkyl-substituted benzophenones for which conflicting thermochemical data were available.

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Prediction of thermodynamic properties: centerpiece approach—how do we avoid confusion and get reliable results?

Cited by 18 publications

References 23 publications

Aprotic Ionic Liquids: A Framework for Predicting Vaporization Thermodynamics

Aprotic Ionic Liquids: A Framework for Predicting Vaporization Thermodynamics

Thermochemistry in the twenty-first century–quo vadis? In silico assisted diagnostics of available thermochemical data

Thermochemistry in 21 st century – Quo Vadis? In silico assisted diagnostics of available thermochemical data

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