Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene
We studied the photolysis of (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene in supercritical CO2 and Xe, as well as in compressed Kr. The compound has good solubility in the mentioned fluids, allowing the photolysis measurements to be performed in CO2 at 1.4 K above Tc and at pressures as low a...
| Autores principales: | , , |
|---|---|
| Publicado: |
2009
|
| Materias: | |
| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v113_n18_p5289_Hoijemberg http://hdl.handle.net/20.500.12110/paper_10895639_v113_n18_p5289_Hoijemberg |
| Aporte de: |
| id |
paper:paper_10895639_v113_n18_p5289_Hoijemberg |
|---|---|
| record_format |
dspace |
| spelling |
paper:paper_10895639_v113_n18_p5289_Hoijemberg2023-06-08T16:06:24Z Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene Hoijemberg, Pablo Ariel Japas, María Laura Aramendía, Pedro Francisco Absorbance Cage effect Compressed gas Constant temperature Critical points Diazene Ethyl radicals Nanosecond laser pulse Nitrogen loss Spectroscopic data Supercritical CO2 Effluent treatment Energy transfer Equations of state Krypton Organic polymers Pulsed laser applications Supercritical fluids Technetium Xenon Photolysis (1 biphenyl 4 yl 1 methylethyl) tert butyl diazene (1-biphenyl-4-yl-1-methylethyl)-tert-butyl diazene biphenyl derivative imide absorption article chemistry gas photolysis solubility Absorption Biphenyl Compounds Gases Imides Photolysis Solubility We studied the photolysis of (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene in supercritical CO2 and Xe, as well as in compressed Kr. The compound has good solubility in the mentioned fluids, allowing the photolysis measurements to be performed in CO2 at 1.4 K above Tc and at pressures as low as 70 bar. We monitored relative cage effect after nanosecond laser pulses by measuring the absorbance at 320 nm (AAtf 0) corresponding to the total amount of out-of-cage 1-biphenyl-4-yl-1-methyl-ethyl radical (BME ·) produced after nitrogen loss of the diazene. In supercritical CO2 and Xe, isothermal values of AAtf 0 showed an increase-decrease behavior with increasing pressure at constant temperature, a typical feature of the transition from the solvent energy transfer to the friction controlled regimes. The comparison of the behavior of AAtf 0 in CO2 at reduced temperatures between 1.004 and 1.027, in Xe, and in Kr points to an absence of enhanced cage effect near the critical point. Compatibility with spectroscopic data is analyzed. © 2009 American Chemical Society. Fil:Hoijemberg, P.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Japas, M.L. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Aramendia, P.F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2009 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v113_n18_p5289_Hoijemberg http://hdl.handle.net/20.500.12110/paper_10895639_v113_n18_p5289_Hoijemberg |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Absorbance Cage effect Compressed gas Constant temperature Critical points Diazene Ethyl radicals Nanosecond laser pulse Nitrogen loss Spectroscopic data Supercritical CO2 Effluent treatment Energy transfer Equations of state Krypton Organic polymers Pulsed laser applications Supercritical fluids Technetium Xenon Photolysis (1 biphenyl 4 yl 1 methylethyl) tert butyl diazene (1-biphenyl-4-yl-1-methylethyl)-tert-butyl diazene biphenyl derivative imide absorption article chemistry gas photolysis solubility Absorption Biphenyl Compounds Gases Imides Photolysis Solubility |
| spellingShingle |
Absorbance Cage effect Compressed gas Constant temperature Critical points Diazene Ethyl radicals Nanosecond laser pulse Nitrogen loss Spectroscopic data Supercritical CO2 Effluent treatment Energy transfer Equations of state Krypton Organic polymers Pulsed laser applications Supercritical fluids Technetium Xenon Photolysis (1 biphenyl 4 yl 1 methylethyl) tert butyl diazene (1-biphenyl-4-yl-1-methylethyl)-tert-butyl diazene biphenyl derivative imide absorption article chemistry gas photolysis solubility Absorption Biphenyl Compounds Gases Imides Photolysis Solubility Hoijemberg, Pablo Ariel Japas, María Laura Aramendía, Pedro Francisco Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene |
| topic_facet |
Absorbance Cage effect Compressed gas Constant temperature Critical points Diazene Ethyl radicals Nanosecond laser pulse Nitrogen loss Spectroscopic data Supercritical CO2 Effluent treatment Energy transfer Equations of state Krypton Organic polymers Pulsed laser applications Supercritical fluids Technetium Xenon Photolysis (1 biphenyl 4 yl 1 methylethyl) tert butyl diazene (1-biphenyl-4-yl-1-methylethyl)-tert-butyl diazene biphenyl derivative imide absorption article chemistry gas photolysis solubility Absorption Biphenyl Compounds Gases Imides Photolysis Solubility |
| description |
We studied the photolysis of (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene in supercritical CO2 and Xe, as well as in compressed Kr. The compound has good solubility in the mentioned fluids, allowing the photolysis measurements to be performed in CO2 at 1.4 K above Tc and at pressures as low as 70 bar. We monitored relative cage effect after nanosecond laser pulses by measuring the absorbance at 320 nm (AAtf 0) corresponding to the total amount of out-of-cage 1-biphenyl-4-yl-1-methyl-ethyl radical (BME ·) produced after nitrogen loss of the diazene. In supercritical CO2 and Xe, isothermal values of AAtf 0 showed an increase-decrease behavior with increasing pressure at constant temperature, a typical feature of the transition from the solvent energy transfer to the friction controlled regimes. The comparison of the behavior of AAtf 0 in CO2 at reduced temperatures between 1.004 and 1.027, in Xe, and in Kr points to an absence of enhanced cage effect near the critical point. Compatibility with spectroscopic data is analyzed. © 2009 American Chemical Society. |
| author |
Hoijemberg, Pablo Ariel Japas, María Laura Aramendía, Pedro Francisco |
| author_facet |
Hoijemberg, Pablo Ariel Japas, María Laura Aramendía, Pedro Francisco |
| author_sort |
Hoijemberg, Pablo Ariel |
| title |
Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene |
| title_short |
Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene |
| title_full |
Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene |
| title_fullStr |
Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene |
| title_full_unstemmed |
Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene |
| title_sort |
cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene |
| publishDate |
2009 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v113_n18_p5289_Hoijemberg http://hdl.handle.net/20.500.12110/paper_10895639_v113_n18_p5289_Hoijemberg |
| work_keys_str_mv |
AT hoijembergpabloariel cageeffectinsupercriticalfluidsandcompressedgasesinthephotolysisofanasymmetricallysubstituteddiazene AT japasmarialaura cageeffectinsupercriticalfluidsandcompressedgasesinthephotolysisofanasymmetricallysubstituteddiazene AT aramendiapedrofrancisco cageeffectinsupercriticalfluidsandcompressedgasesinthephotolysisofanasymmetricallysubstituteddiazene |
| _version_ |
1768542424362123264 |