Sublimation Study of Six 5-Substituted-1,10-Phenanthrolines by Knudsen Effusion Mass Loss and Solution Calorimetry
The vapor pressures of six solid 5-X-1,10-phenanthrolines (where X = Cl, CH<sub>3</sub>, CN, OCH<sub>3</sub>, NH<sub>2</sub>, NO<sub>2</sub>) were determined in suitable temperature ranges by Knudsen Effusion Mass Loss (KEML). From the temperature depe...
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2022-01-01
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| author | Bruno Brunetti Andrea Ciccioli Andrea Lapi Aleksey V. Buzyurov Ruslan N. Nagrimanov Mikhail A. Varfolomeev Stefano Vecchio Ciprioti |
| author_facet | Bruno Brunetti Andrea Ciccioli Andrea Lapi Aleksey V. Buzyurov Ruslan N. Nagrimanov Mikhail A. Varfolomeev Stefano Vecchio Ciprioti |
| author_sort | Bruno Brunetti |
| collection | DOAJ |
| description | The vapor pressures of six solid 5-X-1,10-phenanthrolines (where X = Cl, CH<sub>3</sub>, CN, OCH<sub>3</sub>, NH<sub>2</sub>, NO<sub>2</sub>) were determined in suitable temperature ranges by Knudsen Effusion Mass Loss (KEML). From the temperature dependencies of vapor pressure, the molar sublimation enthalpies, Δ<sub>cr</sub><sup>g</sup><i>H</i><sub>m</sub><sup>0</sup>(⟨<i>T</i>⟩), were calculated at the corresponding average ⟨<i>T</i>⟩ of the explored temperature ranges. Since to the best of our knowledge no thermochemical data seem to be available in the literature regarding these compounds, the Δ<sub>cr</sub><sup>g</sup><i>H</i><sub>m</sub><sup>0</sup>(⟨<i>T</i>⟩) values obtained by KEML experiments were adjusted to 298.15 K using a well known empirical procedure reported in the literature. The standard (<i>p</i><sup>0</sup> = 0.1 MPa) molar sublimation enthalpies, Δ<sub>cr</sub><sup>g</sup><i>H</i><sub>m</sub><sup>0</sup>(298.15 K), were compared with those determined using a recently proposed solution calorimetry approach, which was validated using a remarkable amount of thermochemical data of molecular compounds. For this purpose, solution enthalpies at infinite dilution of the studied 5-chloro and 5-methylphenantrolines in benzene were measured at 298.15 K. Good agreement was found between the values derived by the two different approaches, and final mean values of Δ<sub>cr</sub><sup>g</sup><i>H</i><sub>m</sub><sup>0</sup>(298.15 K) were recommended. Finally, the standard molar entropies and Gibbs energies of sublimation were also derived at <i>T</i> = 298.15 K. The volatilities of the six compounds were found to vary over a range of three orders of magnitude in the explored temperature range. The large difference in volatility was analyzed in the light of enthalpies and entropies of sublimation. The latter was tentatively put in relation to the rotational contribution of the substituent group on the phenanthroline unit. |
| first_indexed | 2024-03-09T22:02:14Z |
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| spelling | doaj.art-1070716b6d5449a28cbd8dd5d83219f22023-11-23T19:47:27ZengMDPI AGEntropy1099-43002022-01-0124219210.3390/e24020192Sublimation Study of Six 5-Substituted-1,10-Phenanthrolines by Knudsen Effusion Mass Loss and Solution CalorimetryBruno Brunetti0Andrea Ciccioli1Andrea Lapi2Aleksey V. Buzyurov3Ruslan N. Nagrimanov4Mikhail A. Varfolomeev5Stefano Vecchio Ciprioti6Istituto per lo Studio dei Materiali Nanostrutturati, Consiglio Nazionale delle Ricerche, Dipartimento di Chimica, Sapienza Università di Roma, P.le A. Moro 5, 00185 Rome, ItalyDipartimento di Chimica, Sapienza Università di Roma, P.le A. Moro 5, 00185 Rome, ItalyDipartimento di Chimica, Sapienza Università di Roma, P.le A. Moro 5, 00185 Rome, ItalyA.M. Butlerov Chemical Institute, Kazan Federal University, Kremlevskaja Str. 18, 420008 Kazan, RussiaA.M. Butlerov Chemical Institute, Kazan Federal University, Kremlevskaja Str. 18, 420008 Kazan, RussiaDepartment of Petroleum Engineering, Institute of Geology and Petroleum Technologies, Kazan Federal University, Kremlevskaja Str. 18, 420008 Kazan, RussiaDipartimento di Scienze di Base ed Applicate per l’Ingegneria (S.B.A.I.), Sapienza University of Rome, Via del Castro Laurenziano 7, Building RM017, 00161 Rome, ItalyThe vapor pressures of six solid 5-X-1,10-phenanthrolines (where X = Cl, CH<sub>3</sub>, CN, OCH<sub>3</sub>, NH<sub>2</sub>, NO<sub>2</sub>) were determined in suitable temperature ranges by Knudsen Effusion Mass Loss (KEML). From the temperature dependencies of vapor pressure, the molar sublimation enthalpies, Δ<sub>cr</sub><sup>g</sup><i>H</i><sub>m</sub><sup>0</sup>(⟨<i>T</i>⟩), were calculated at the corresponding average ⟨<i>T</i>⟩ of the explored temperature ranges. Since to the best of our knowledge no thermochemical data seem to be available in the literature regarding these compounds, the Δ<sub>cr</sub><sup>g</sup><i>H</i><sub>m</sub><sup>0</sup>(⟨<i>T</i>⟩) values obtained by KEML experiments were adjusted to 298.15 K using a well known empirical procedure reported in the literature. The standard (<i>p</i><sup>0</sup> = 0.1 MPa) molar sublimation enthalpies, Δ<sub>cr</sub><sup>g</sup><i>H</i><sub>m</sub><sup>0</sup>(298.15 K), were compared with those determined using a recently proposed solution calorimetry approach, which was validated using a remarkable amount of thermochemical data of molecular compounds. For this purpose, solution enthalpies at infinite dilution of the studied 5-chloro and 5-methylphenantrolines in benzene were measured at 298.15 K. Good agreement was found between the values derived by the two different approaches, and final mean values of Δ<sub>cr</sub><sup>g</sup><i>H</i><sub>m</sub><sup>0</sup>(298.15 K) were recommended. Finally, the standard molar entropies and Gibbs energies of sublimation were also derived at <i>T</i> = 298.15 K. The volatilities of the six compounds were found to vary over a range of three orders of magnitude in the explored temperature range. The large difference in volatility was analyzed in the light of enthalpies and entropies of sublimation. The latter was tentatively put in relation to the rotational contribution of the substituent group on the phenanthroline unit.https://www.mdpi.com/1099-4300/24/2/1925-substituted-1,10-phenanthrolinesvapor pressureKnudsen Effusionsolution calorimetrystandard molar sublimation enthalpystandard molar sublimation entropy |
| spellingShingle | Bruno Brunetti Andrea Ciccioli Andrea Lapi Aleksey V. Buzyurov Ruslan N. Nagrimanov Mikhail A. Varfolomeev Stefano Vecchio Ciprioti Sublimation Study of Six 5-Substituted-1,10-Phenanthrolines by Knudsen Effusion Mass Loss and Solution Calorimetry Entropy 5-substituted-1,10-phenanthrolines vapor pressure Knudsen Effusion solution calorimetry standard molar sublimation enthalpy standard molar sublimation entropy |
| title | Sublimation Study of Six 5-Substituted-1,10-Phenanthrolines by Knudsen Effusion Mass Loss and Solution Calorimetry |
| title_full | Sublimation Study of Six 5-Substituted-1,10-Phenanthrolines by Knudsen Effusion Mass Loss and Solution Calorimetry |
| title_fullStr | Sublimation Study of Six 5-Substituted-1,10-Phenanthrolines by Knudsen Effusion Mass Loss and Solution Calorimetry |
| title_full_unstemmed | Sublimation Study of Six 5-Substituted-1,10-Phenanthrolines by Knudsen Effusion Mass Loss and Solution Calorimetry |
| title_short | Sublimation Study of Six 5-Substituted-1,10-Phenanthrolines by Knudsen Effusion Mass Loss and Solution Calorimetry |
| title_sort | sublimation study of six 5 substituted 1 10 phenanthrolines by knudsen effusion mass loss and solution calorimetry |
| topic | 5-substituted-1,10-phenanthrolines vapor pressure Knudsen Effusion solution calorimetry standard molar sublimation enthalpy standard molar sublimation entropy |
| url | https://www.mdpi.com/1099-4300/24/2/192 |
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