Award Abstract # 0533634
Heterogeneous Organic Oxidation Reactions of Atmospheric Importance Studied by Broadband Vibrational Sum Frequency and Second Harmonic Generation

NSF Org: AGS
Division of Atmospheric and Geospace Sciences
Recipient: NORTHWESTERN UNIVERSITY
Initial Amendment Date: March 31, 2006
Latest Amendment Date: April 13, 2009
Award Number: 0533634
Award Instrument: Continuing Grant
Program Manager: Anne-Marie Schmoltner
AGS
 Division of Atmospheric and Geospace Sciences
GEO
 Directorate for Geosciences
Start Date: April 1, 2006
End Date: March 31, 2010 (Estimated)
Total Intended Award Amount: $0.00
Total Awarded Amount to Date: $150,001.00
Funds Obligated to Date: FY 2006 = $49,952.00
FY 2007 = $49,746.00

FY 2008 = $50,303.00
History of Investigator:
  • Franz Geiger (Principal Investigator)
    f-geiger@northwestern.edu
Recipient Sponsored Research Office: Northwestern University
633 CLARK ST
EVANSTON
IL  US  60208-0001
(312)503-7955
Sponsor Congressional District: 09
Primary Place of Performance: Northwestern University
633 CLARK ST
EVANSTON
IL  US  60208-0001
Primary Place of Performance
Congressional District:
09
Unique Entity Identifier (UEI): EXZVPWZBLUE8
Parent UEI:
NSF Program(s): Atmospheric Chemistry,
ANALYTICAL SEPARATIONS & MEAS.
Primary Program Source: app-0106 
app-0107 

01000809DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 0000, 4444, OTHR
Program Element Code(s): 152400, 197400
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.050

ABSTRACT

Professor Franz Geiger of Northwestern University is supported by the Atmospheric Chemistry program in the Division of Atmospheric Sciences and the Analytical and Surface Chemistry program in the Division of Chemistry to investigate the chemistry of organic compounds at the surface of atmospheric aerosols and their chemical reactions. Partially oxidized organic species present in the tropospheric gas phase can bind to aerosol surfaces through their polar ends, with their remaining double bonds exposed to the gas phase for reaction with atmospheric oxidants. In this laboratory study, heterogeneous carbon-carbon double bond oxidation reactions of cyclic and acyclic surface-bound olefins will be studied under conditions relevant to the atmosphere, specifically in the presence of ppb-levels of ozone and at a total pressure of 1 atm. Tailored cyclic and acyclic organic compounds will be tethered to solid substrates through organosilane chemistry, and then exposed to ozone. The rate of ozone uptake will be determined. Nonlinear optical spectroscopy methods that are sensitive to interfaces only, specifically second harmonic generation (SHG) and vibrational sum frequency generation (VSFG), will be used to probe the interaction of ozone with the surface-active organic compounds. This will allow identification of the surface-bound reactants and the reaction intermediates and products. Reaction products will also be studied using a chemical ionization-mass spectrometer (CIMS).

This study will provide new insights into the mechanisms of heterogeneous organic oxidation reactions at solid/air interfaces and detailed, molecular-level information on chemical fate of organic compounds and ozone in the atmosphere. This project will support one graduate student and will be linked to outreach activities by the principal investigator aimed at K-12 students and the public.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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Andrea B. Voges, Grace Yin, Julianne M. Gibbs-Davis, Robert B. Lettan II, Paul A. Bertin, Rachel C. Pike, SonBinh T. Nguyen, Karl A. Scheidt, and Franz M. Geiger ""Insights into Heterogeneous Atmospheric Oxidation Chemistry: Development of a Tailor-" Feature Article and Cover of the Feb 2007 issue of J. Phys. Chem. C , v.111 , 2007 , p.1567
Catherine M. Schmidt, Aditya Savara, Eric Weitz, and Franz M. Geiger ""Enthalpy and Entropy of the Indoor Air Pollutant Acetone Interacting with Degussa P25 TiO2" J. Phys. Chem. C , v.111 , 2007 , p.8260
Catherine M. Schmidt, Avram Buchbinder, Eric Weitz, and Franz M. Geiger ""Photochemistry of the Indoor Air Pollutant Acetone on Degussa P25 TiO2 Studied by Chemical Ionization Mass Spectrometry"" J. Phys. Chem. A , v.111 , 2008 , p.13023
Catherine M. Schmidt, Eric Weitz, and Franz M. Geiger ""Interaction of the Indoor Air Pollutant Acetone with Degussa P25 TiO2 Studied by Chemical" Langmuir , v.22 , 2006 , p.9642
Franz M. Geiger ""Second Harmonic Generation, Sum Frequency Generation, and Chi(3): Dissecting Environmental Interfaces with a Nonlinear Optical Swiss Army Knife"" Invited Contribution for Annual Review of Physical Chemistry, (vol. 60) , v.60 , 2009 , p.61
Grace Y. Stokes, Avram Buchbinder, Julianne M. Gibbs-Davis, and Franz M. Geiger ""Heterogeneous Ozone Oxidation Reactions of 1-Pentene, 2-Hexene, Cyclopentene, Cyclohexene, and a Menthenol Derivative Studied by Sum Frequency Generation"" J. Phys. Chem. C , v.112 , 2008 , p.11688
Grace Y. Stokes, Avram M. Buchbinder, Julianne M. Gibbs, Karl A. Scheidt, and Franz M. Geiger ""Chemically Diverse Environmental Interfaces and Their Reactions with Ozone Studied by Vibrational Sum Frequency Generation"" Invited Contribution for Vibrational Spectroscopy , v.50 , 2009 , p.86
Grace Y. Stokes, Ehow H. Chen, Avram M. Buchbinder, Alison Keeley, and Franz M. Geiger* ""Atmospheric Heterogeneous Stereochemistry"" J. Am. Chem. Soc. , v.131 , 2009 , p.13733
Grace Y. Stokes, Ehow H. Chen, Stephanie R. Walter, and Franz M. Geiger* ""Two Reactivity Modes in the Heterogeneous Cyclohexene Ozonolysis Under Tropospherically Relevant Ozone-Rich and Ozone-Limited Conditions"" J. Phys. Chem. A , v.113 , 2009 , p.8985

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