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Cited by 52Atmospheric chemistry and aerosolsAdvanced Combustion Engine TechnologiesAtmospheric Ozone and Climate

Gas-Phase Rate Coefficients for the OH + n-, i-, s-, and t-Butanol Reactions Measured Between 220 and 380 K: Non-Arrhenius Behavior and Site-Specific Reactivity

McGillen, Max R., Baasandorj, Munkhbayar, Burkholder, James B.·2013·The Journal of Physical Chemistry A
DOI 10.1021/jp402702u
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Abstract

Butanol (C4H9OH) is a potential biofuel alternative in fossil fuel gasoline and diesel formulations. The usage of butanol would necessarily lead to direct emissions into the atmosphere; thus, an understanding of its atmospheric processing and environmental impact is desired. Reaction with the OH radical is expected to be the predominant atmospheric removal process for the four aliphatic isomers of butanol. In this work, rate coefficients, k, for the gas-phase reaction of the n-, i-, s-, and t-butanol isomers with the OH radical were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH radicals and laser induced fluorescence to monitor its temporal profile. Rate coefficients were measured over the temperature range 221-381 K at total pressures between 50 and 200 Torr (He). The reactions exhibited non-Arrhenius behavior over this temperature range and no dependence on total pressure with k(296 K) values of (9.68 ± 0.75), (9.72 ± 0.72), (8.88 ± 0.69), and (1.04 ± 0.08) (in units of 10(-12) cm(3) molecule(-1) s(-1)) for n-, i-, s-, and t-butanol, respectively. The quoted uncertainties are at the 2σ level and include estimated systematic errors. The observed non-Arrhenius behavior is interpreted here to result from a competition between the available H-atom abstraction reactive sites, which have different activation energies and pre-exponential factors. The present results are compared with results from previous kinetic studies, structure-activity relationships (SARs), and theoretical calculations and the discrepancies are discussed. Results from this work were combined with available high temperature (1200-1800 K) rate coefficient data and room temperature reaction end-product yields, where available, to derive a self-consistent site-specific set of reaction rate coefficients of the form AT(n) exp(-E/RT) for use in atmospheric and combustion chemistry modeling.

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  • The relatively short lifetime of i-butanol (a few days) means its emissions and oxidation products are likely to impact local and regional air quality.

    “The relatively short lifetime of i-butanol (a few days) [143] mean that its emission and its oxidation products are likely to impact local and regional air quality.”

    From Investigation of Biofuel as a Potential Renewable Energy Source (2021) · cites this paper as [143]

  • i-Butanol is predominantly removed from the atmosphere via reaction with the OH radical, a highly site-specific process.

    “Once emitted, i-butanol is predominantly removed from the atmosphere via reaction with the OH radical, which is a highly sitespecific process.”

    From Investigation of Biofuel as a Potential Renewable Energy Source (2021) · cites this paper as [143]

  • Photo-oxidation products of i-butanol can influence tropospheric ozone, SOA, and PANs.

    “Once released into the atmosphere, the photo-oxidation products of i-butanol can influence tropospheric ozone, as well as other secondary pollutants such as secondary organic aerosols (SOA) and PANs.”

    From Investigation of Biofuel as a Potential Renewable Energy Source (2021) · cites this paper as [143]

  • The OH radical reaction with i-butanol has competing pathways leading to different stable end products and potentially different impacts on atmospheric composition.

    “There are a number of competing pathways by which this reaction can proceed, thus leading to the formation of different stable end product(s) (see Figure 6) and potentially, different impacts on atmospheric composition.”

    From Investigation of Biofuel as a Potential Renewable Energy Source (2021) · cites this paper as [143]

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Authors
McGillen, M. R., Baasandorj, M., & Burkholder, J. B.
Affiliations
National Oceanic and Atmospheric Administration (US)
Corresponding author
Burkholder, James B.
ORCID
Venue
The Journal of Physical Chemistry A
Publisher
American Chemical Society (ACS)
Published
2013-05-22
Volume
117
Issue
22
Pages
4636-4656
ISSN
  • 1089-5639 (ISSN-L)
  • 1520-5215
DOI
10.1021/jp402702u
OpenAlex
W2326999335
Cited by
52
References
51
Citations by year
2026: 4 · 2025: 3 · 2024: 3 · 2023: 2 · 2022: 4 · 2021: 11 · 2020: 8 · 2018: 2 · 2017: 2 · 2016: 2 · 2015: 6 · 2014: 3 · 2013: 2
FWCI
2.82
Type
journal article
Language
en
Open access
closed
Locations
  • The Journal of Physical Chemistry A (publishedVersion)
  • PubMed (publishedVersion)
Topics
  • Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Atmospheric chemistry and aerosols
  • Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Advanced Combustion Engine Technologies
  • Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Atmospheric Ozone and Climate
Keywords
butanol, hydroxyl radicals, non-Arrhenius behavior, site-specific reactivity, H-atom abstraction, n-butanol, tert-butanol, butanol isomers, atmospheric chemistry, biofuel emissions, structure-activity relationship, reaction kinetics, atmospheric chemistry modeling, combustion chemistry

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