Direct effect of fast electrons on hexafluoroacetylacetone

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription Access

Abstract

The radiolysis of liquid and boiling hexafluoroacetylacetone was studied. The structure of the main radiolysis products indicates the predominance of C–CF3 and C–F bond cleavages. Ten compounds are formed, including monoketones, trifluoroacetic acid, keto alcohols, and tautomeric tetraketones. Carbon monoxide is the main gaseous product and its yield increases under boiling conditions. The initial yield of hexafluoroacetylacetone degradation is 0.29 ± 0.2 and 0.32 ± 0.2 µmol J-1 at 293 and 343 K, respectively. No accumulation of free HF is observed at low doses. The products of radiolysis are less diverse than in acetylacetone, which is due to the increased “cage” effect, the increase in the Onsager radius and the ability of trifluoromethyl groups to dissipate excitation energy.

Full Text

Restricted Access

About the authors

S. I. Vlasov

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, RAS

Email: ponomarev@ipc.rssi.ru
Russian Federation, Moscow

E. M. Kholodkova

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, RAS

Email: ponomarev@ipc.rssi.ru
Russian Federation, Moscow

A. V. Ponomarev

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, RAS

Author for correspondence.
Email: ponomarev@ipc.rssi.ru
Russian Federation, Moscow

References

  1. Utke I., Swiderek P., Höflich K., Madajska K., Jurczyk J., Martinović P., Szymańska I.B. // Coord. Chem. Rev. 2022. V. 458. P. 213851.
  2. Travnikov S.S., Fedoseev E.V., Davydov A.V., Myasoedov B.F. // J. Radioanal. Nucl. Chem. Lett. 1985. V. 93. P. 227.
  3. Gandomi F., Vakili M., Takjoo R., Tayyari S.F. // J. Mol. Struct. 2022. V. 1248. P. 131347.
  4. Lutoshkin M.A., Taydakov I.V. // J. Solution Chem. 2023. V. 52. P. 304.
  5. Liu H., Wang X., Lan Z., Xu H. // Sep. Purif. Technol. 2021. V. 262. P. 118309.
  6. Shahbazi S., Stratz S.A., Auxier J.D., Hanson D.E., Marsh M.L., Hall H.L. // J. Radioanal. Nucl. Chem. 2017. V. 311. P. 617.
  7. De Vries B., Muyskens M. // Comput. Theor. Chem. 2016. V. 1097. P. 15.
  8. Haugen E.A., Hait D., Scutelnic V., Xue T., Head-Gordon M., Leone S.R. // J. Phys. Chem. A 2023. V. 127. P. 634.
  9. Lugo P.L., Straccia V.G., Rivela C.B., Patroescu-Klotz I., Illmann N., Teruel M.A., Wiesen P., Blanco M.B. // Chemosphere 2022. V. 286. P. 131562.
  10. Gutiérrez-Quintanilla A., Chevalier M., Platakyté R., Ceponkus J., Crépin C. // Eur. Phys. J. D 2023. V. 77. P. 158.
  11. Vlasov S.I., Smirnova A.A., Ponomarev A.V., Uchkina D.A., Sholokhova A.Yu., Mitrofanov A.A. // High Energy Chem. 2023. V. 57. P. 258.
  12. Gromov A.A., Zhanzhora A.P., Kovalenko O.I. // Meas. Stand. Ref. Mater. 2022. V. 17. P. 23.
  13. Uchkina D.A., Ponomarev A.V. // Mendeleev Commun. 2023. V. 33. P. 390.
  14. Vlasov S.I., Kholodkova E.M., Ponomarev A.V. // High Energy Chem. 2021. V. 55. P. 393.
  15. Traven V.F. Frontier orbitals and properties of organic molecules (Ellis Horwood Series in Organic Chemistry) / Mellor, J. ed. New York: Ellis Horwood Ltd, 1992.
  16. Woods R., Pikaev A. Applied radiation chemistry. Radiation processing. NY: Wiley, 1994.
  17. Shuman N.S., Miller T.M., Friedman J.F., Viggiano A.A., Maergoiz A.I., Troe J. // J. Chem. Phys. 2011. V. 135. P. 054306.
  18. Ómarsson B., Engmann S., Ingólfsson O. // RSC Adv. 2014. V. 4. P. 33222.
  19. Zhestkova T.P., Zhukova T.N., Ponomarev A.V., Tananaev I.G. // Mendeleev Commun. 2008. V. 18. P. 338.
  20. Disselkoen K.R., Alsum J.R., Thielke T.A., Muyskens M.A. // Chem. Phys. Lett. 2017. V. 672. P. 112.
  21. Belova E.V., Ponomarev A.V., Smirnov A.V. // J. Radioanal. Nucl. Chem. 2022. V. 331. P. 4405.

Supplementary files

Supplementary Files
Action
1. JATS XML
2. Fig. 1. Radiation-chemical yields of G primary products in HFAA.

Download (164KB)
3. Formula 1

Download (23KB)
4. Fig. 2. Cationic mass spectra of the enol and diketo forms of HFAA

Download (107KB)
5. Formula 2

Download (17KB)
6. Formula 3

Download (20KB)
7. Formula 4

Download (25KB)
8. Formula 5

Download (17KB)
9. Formula 6

Download (27KB)
10. Formula 7

Download (27KB)
11. Formula 8

Download (38KB)
12. Formula 9

Download (17KB)
13. Formula 10

Download (21KB)
14. Formula 11

Download (17KB)
15. Formula 12

Download (25KB)
16. Formula 13

Download (20KB)
17. Formula 14

Download (20KB)
18. Formula 15

Download (19KB)
19. Formula 16

Download (20KB)
20. Formula 17

Download (24KB)
21. Formula 18

Download (28KB)
22. Formula 19

Download (19KB)
23. Formula 20

Download (19KB)
24. Formula 21

Download (20KB)
25. Formula 22

Download (36KB)
26. Formula 23

Download (33KB)
27. Formula 24

Download (20KB)

Copyright (c) 2024 Russian Academy of Sciences