novel applications of a shape-sensitive detector 3: modeling combustion chemistry through an...
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NOVEL APPLICATIONS OF A SHAPE-SENSITIVE DETECTOR 3:
MODELING COMBUSTION CHEMISTRY THROUGH AN ELECTRIC DISCHARGE SOURCE
Giana Storck
Purdue UniversityDepartment of Chemistry
560 Oval Dr, West Lafayette, IN 47907-2084
Chandana KarunatilakaPost-Doc
Amanda ShirarGraduate Student
Kelly HotoppGraduate Student
Undergraduates: Ricky Crawley Jr., Erin Blaze Biddle
Brian C. Dian
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Combustion ChemistryThe Chemistry of Combustive Materials
More efficient ways to burn fuelCleaner Chemistry throughout the combustion process (soot formation)
CharacterizationQuantitative (Rate Constants) and Qualitative (Product Identification)
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Common Methods for Studying Combustion Chemistry
Fluorescence Based
Very Sensitive
Appropriate chromophore necessary
Not discriminatory
Mass based
Mass Selective
Doesn’t reveal bond connectivity
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Using Our Experimental SetupBased on Rotational Spectroscopy
Only need a dipole moment
Shape sensitive
Isomeric (bond connectivity) and
Conformational (molecular shape)
Quick (10,000 avg. in ~20 minutes)
With 20 μs gate, ~170,000 data channels
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Shape Sensitive TechniqueRotational Constants 1/r2
A*: 11479 MHz B: 3963 MHz C: 3819 MHz
A*: 13950 MHzB: 3309 MHzC: 3046 MHz
*H. N. Volltrauer and R. H. Schwendeman, J. Chem. Phys. 54 (1971) 260
Cyclopropanecarboxaldehyde
CisTrans
μ= reduced massr=nuclear displacement from center of mass
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Experimental Setup
Reaction initiated via Penning Ionization of Ar bath.
Hot products cooled in supersonic expansion
Typical Discharge Voltage +/-500 V
Discharged pulsed 100 μs (Expansion > 1ms)
Pulsed Valve Body
Discharge Housing
Electrodes
Insulator (Delrin)
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Chirped Pulse FTMW Discharge Setup
18.9 GHzPDRO
12 GHz Oscilloscope
(40 Gs/s)
ArbitraryWaveformGenerator
100 MHz Quartz Oscillator
Chirped Pulse1.875-4.675 GHz
7.5-18.5GHz
Free InductionDecay
x4
20 dB
Discharge Nozzle
Discharge Pulse
Generator
Timing Control Box
200W
Sample + Ar
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Experimental Timing
Sample Pulse Drift Time Acquisition
Discharge
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2,3-Dihydrofuran 2,3-DHF is found in petroleum and other fuels
Unimolecular rearrangement to Cyclopropanecarboxaldehyde (CPCA) and Crotonaldehyde (CA)
Characterization of Products through rotational spectrum.
Do we identify any new species?
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A: 8084B: 7785C: 4201
000-101
Ground State Spectrum of 2,3-DHF
Corvellati, R.; Esposti, A.; Lister, D.; Lopez, J.; Alonso, J.; J. Mol. Struct. 147 (1986) 255
A: 8084B: 7785C: 4201
101-000
321-322
211-212
Near Oblate TopA-type Spectrum
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Valve Difference
Using Old Discharge Valve Holder
New Discharge Nozzle
Old Discharge Nozzle
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Discharge Spectrum
Cyclopropane carboxaldehyde (CPCA)
Crotonaldehyde (CA)
A. Lifshitz, M. Bidani; J. Phys. Chem., 93, (1989), pp. 1139-1144.
Trans CPCACis CPCATrans CATrans AcroleinCis AcroleinPropenePropyneFormaldehyde
Products found after a gas was put through a single pulse shock tube and were analyzed using GC/MS
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Results
Experimental
SPCAT
10,000 acquisitions~20 min
Trans CPCACis CPCATrans CATrans AcroleinCis AcroleinPropenePropyneFormaldehyde
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Unidentified Species
SPCAT
A: 19383B: 2356C: 2316
ΔJ=3→4Big Molecule
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Theoretical Reaction Surfaces
Adapted from:F. Dubnikova, A. Lifshitz, J. Phys. Chem. A; v.106 (2002) pp. 1026-1034.
Barrier ~ 20,000 cm-1
ΔE
(kca
l/mo
l)
CyclopropanecarboxaldehydeCrotonaldehyde
Transitions found using STQN method and verified using IRC at B3LYP level
ΔE
(kca
l/mo
l) Cis!
ΔE
(kca
l/mo
l)
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CA vs. CPCA Torsional PotentialB3LYP/6-31+G**
*1550 cm-1 *1532 cm-1
**2034 cm-1 **1920 cm-1
2117 cm-1 2076 cm-1
E = 689 cm-1
B3LYP/6-31+G**3493 cm-1 2804 cm-1
*H. N. Volltrauer and R. H. Schwendeman, J. Chem. Phys. 54 (1971) 260
ΔE= 57 cm-1
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Trans:A: 32636B: 2183C: 2073
202-101
303-202
404-303
Cis:A: 19186B: 2609C: 2330
202-101
303-202
404-303
202-101 303-202
10,000 acquisitions~20 min.
Ground State Rotational Spectrum of Crotonaldehyde
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Unidentified Species
SPCAT
Unidentified Species:A: 19383B: 2356C: 2316
Cis Crotonaldehyde:A: 19186B: 2609C: 2330
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Summary What did we learn?
1) It’s not Cis-Crotonaldehyde2) Near Prolate Top
-structure is something like CA3) Splitting on K1 bands suggest it has a
methyl rotor4) Biggest shift along the B-moment
Our best guess at this time is that it could be a radical species
But:-net increase in mass-no evidence for spin-rotation coupling
Argon Cluster?
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Some Future WorkQuantitativeUse intensity information to get
concentrations and possibly rate information
Using different chemicals (dimolecular reactions)
Benzyne+ oxygen
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Acknowledgements
Dian Group
Dr. Brian DianDr. Chandana KarunatilakaAmanda ShirarKelly HotoppRicky CrawleyErin Blaze Biddle
Funding
ACS- PRF G