CoChat
Sign Up
Cited by 15Atmospheric chemistry and aerosolsAdvanced Combustion Engine TechnologiesAtmospheric Ozone and Climate

Experimentally Determined Site-Specific Reactivity of the Gas-Phase OH and Cl + i-Butanol Reactions Between 251 and 340 K

McGillen, Max R., Tyndall, Geoffrey S., Orlando, John J., Pimentel, Andre S., Medeiros, Diogo J., Burkholder, James B.·2016·The Journal of Physical Chemistry A
DOI 10.1021/acs.jpca.6b09266
Open this paper in CoChat — free account

Abstract

Product branching ratios for the gas-phase reactions of i -butanol, (CH 3 ) 2 CHCH 2 OH, with OH radicals (251, 294, and 340 K) and Cl atoms (294 K) were quantified in an environmental chamber study and used to interpret i -butanol site-specific reactivity. i -Butyraldehyde, acetone, acetaldehyde, and formaldehyde were observed as major stable end products in both reaction systems with carbon mass balance indistinguishable from unity. Product branching ratios for OH oxidation were found to be temperature-dependent with the α, β, and γ channels changing from 34 ± 6 to 47 ± 1%, from 58 ± 6 to 37 ± 9%, and from 8 ± 1 to 16 ± 4%, respectively, between 251 and 340 K. Recommended temperature-dependent site-specific modified Arrhenius expressions for the OH reaction rate coefficient are (cm 3 molecule –1 s –1 ): k α ( T ) = 8.64 × 10 –18 × T 1.91 exp(666/ T ); k β ( T ) = 5.15 × 10 –19 × T 2.04 exp(1304/ T ); k γ ( T ) = 3.20 × 10 –17 × T 1.78 exp(107/ T ); k OH ( T ) = 2.10 × 10 –18 × T 2 exp(−23/ T ), where k Total ( T ) = k α ( T ) + k β ( T ) + k γ ( T ) + k OH ( T ). The expressions were constrained using the product branching ratios measured in this study and previous total phenomenological rate coefficient measurements. The site-specific expressions compare reasonably well with recent theoretical work. It is shown that use of i -butanol would result in acetone as the dominant degradation product under most atmospheric conditions.

Integrity signals

Registry

Crossref · 10.1021/acs.jpca.6b09266

Cites

23 of 23 references verified0 citation errors · 0 not checkable

Statistics

Recomputing p-values needs the paper’s full text.

Claims the paper makes

This paper’s full text isn’t openly available, so its claims and self-check weren’t run. The registry and citation checks still apply.

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • 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 [144]

  • 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 [144]

  • 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 [144]

Cites

Flagged first, then by citations

Cited by

Sorted by citations

Related

Authors
McGillen, M. R., Tyndall, G. S., Orlando, J. J., Pimentel, A. S., Medeiros, D. J., & Burkholder, J. B.
Affiliations
  • National Oceanic and Atmospheric Administration (US)
  • NSF National Center for Atmospheric Research (US)
  • Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro, Rio de Janeiro, Brazil
  • Pontifícia Universidade Católica do Rio de Janeiro (BR)
Corresponding author
  • Tyndall, Geoffrey S.
  • Burkholder, James B.
ORCID
Venue
The Journal of Physical Chemistry A
Publisher
American Chemical Society (ACS)
Published
2016-12-08
Volume
120
Issue
50
Pages
9968-9981
ISSN
  • 1089-5639 (ISSN-L)
  • 1520-5215
DOI
10.1021/acs.jpca.6b09266
OpenAlex
W2557023574
Cited by
15
References
23
Citations by year
2025: 1 · 2024: 5 · 2023: 1 · 2021: 4 · 2020: 2 · 2019: 1 · 2018: 1
FWCI
0.41
Type
journal article
Language
en
Open access
closed
Locations
  • The Journal of Physical Chemistry A (publishedVersion)
  • PubMed (publishedVersion)
  • Explore Bristol Research (submittedVersion)
Funders
National Oceanic and Atmospheric Administration
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
site-specific reactivity, hydroxyl radical oxidation, chlorine atom oxidation, product branching ratios, temperature dependence, acetone, acetaldehyde, formaldehyde

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review