| dc.date.accessioned |
2016-11-02T10:19:57Z |
und |
| dc.date.accessioned |
2017-10-24T12:19:25Z |
|
| dc.date.available |
2016-11-02T10:19:57Z |
und |
| dc.date.available |
2017-10-24T12:19:25Z |
|
| dc.date.issued |
2016-11-02T10:19:57Z |
|
| dc.identifier.uri |
http://radr.hulib.helsinki.fi/handle/10138.1/5819 |
und |
| dc.identifier.uri |
http://hdl.handle.net/10138.1/5819 |
|
| dc.title |
Kinetics and Thermochemistry of the Reactions of Propargyl-Type Radicals with Molecular Oxygen |
en |
| ethesis.discipline |
Physical Chemistry |
en |
| ethesis.discipline |
Fysikaalinen kemia |
fi |
| ethesis.discipline |
Fysikalisk kemi |
sv |
| ethesis.discipline.URI |
http://data.hulib.helsinki.fi/id/Ce448602-69e9-456c-b052-430133e5dbe6 |
|
| ethesis.department.URI |
http://data.hulib.helsinki.fi/id/c2dd677c-da9c-4011-94b0-27b1585ac1cb |
|
| ethesis.department |
Kemiska institutionen |
sv |
| ethesis.department |
Department of Chemistry |
en |
| ethesis.department |
Kemian laitos |
fi |
| ethesis.faculty |
Matematisk-naturvetenskapliga fakulteten |
sv |
| ethesis.faculty |
Matemaattis-luonnontieteellinen tiedekunta |
fi |
| ethesis.faculty |
Faculty of Science |
en |
| ethesis.faculty.URI |
http://data.hulib.helsinki.fi/id/8d59209f-6614-4edd-9744-1ebdaf1d13ca |
|
| ethesis.university.URI |
http://data.hulib.helsinki.fi/id/50ae46d8-7ba9-4821-877c-c994c78b0d97 |
|
| ethesis.university |
Helsingfors universitet |
sv |
| ethesis.university |
University of Helsinki |
en |
| ethesis.university |
Helsingin yliopisto |
fi |
| dct.creator |
Pekkanen, Timo Theodor |
|
| dct.issued |
2016 |
|
| dct.language.ISO639-2 |
eng |
|
| dct.abstract |
The oxygen reactions of hydrocarbon radicals are important both in combustion and atmospheric chemistry. In this thesis I have studied the oxygen reactions of propagyl-type radicals (propargyl, 1-methylpropargyl, 3-methylpropargyl and
3-ethylpropargyl). Propargyl radical (2-propyn-1-yl) is an alkyl radical with the structure H3C≡C–CH2● . Because these radicals are resonance stabilised, their oxygen reactions are relatively slow. This means that in a combustion environment they might reach an high enough concentration for their self-reactions to become important. The self-reactions of unsaturated radicals are the first step in the formation of polyaromatic hydrocarbons.
I measured the rate coefficients and equilibrium constants for the oxygen reactions of 3-methylpropargly and 3-ethylpropargly at low pressures (0.2 – 3 Torr) using a tubular flow reactor coupled to a resonance-gas-discharge-lamp photoionisation mass spectrometer (PIMS). Laser photolysis was used to generate the radicals. I have compared my experimental results to previous studies done for the propargyl + O2 and 1-methylpropargyl + O2 reactions. I reanalysed the equilibrium data from these previous studies with an improved kinetic mechanism.
At temperatures below 500 K the reactions were found to be dependent on bath gas pressure and they also had negative temperature dependence. The reactivity order was found to be 3-ethylpropargyl > 3-methylpropargyl ≈ 1-methylpropargyl > propargyl. Standard reaction enthalpies and entropies are reported for all four reactions. The experimental results were combined with quantum chemical computations. |
en |
| dct.language |
en |
|
| ethesis.language.URI |
http://data.hulib.helsinki.fi/id/languages/eng |
|
| ethesis.language |
English |
en |
| ethesis.language |
englanti |
fi |
| ethesis.language |
engelska |
sv |
| ethesis.thesistype |
pro gradu-avhandlingar |
sv |
| ethesis.thesistype |
pro gradu -tutkielmat |
fi |
| ethesis.thesistype |
master's thesis |
en |
| ethesis.thesistype.URI |
http://data.hulib.helsinki.fi/id/thesistypes/mastersthesis |
|
| dct.identifier.urn |
URN:NBN:fi-fe2017112251543 |
|
| dc.type.dcmitype |
Text |
|
