The application of total hydrocarbon flame ionization detectors to the analysis of hydrocarbon mixtures from motor vehicles, with and without catalytic emission control

Black, Frank; High, Larry E.; Sigsby, John E.

doi:10.1007/bf00431579

Cited by 12 publications

(4 citation statements)

References 9 publications

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“…There are minor differences in response for each hydrocarbon in each system when compared to propane. There are also potential matrix problems due to the presence of oxygen in the FID (13,14). The summation of the GC speciation may not reflect the presence of compounds with high molecular weight (above Cn), resulting in a low total hydrocarbon quantitation.…”

Section: Resultsmentioning

confidence: 99%

Volatile organic compound emissions from 46 in-use passenger cars

Sigsby¹,

Tejada²,

Ray³

et al. 1987

Environ. Sci. Technol.

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178

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Section: Resultsmentioning

confidence: 99%

Volatile organic compound emissions from 46 in-use passenger cars

Sigsby¹,

Tejada²,

Ray³

et al. 1987

Environ. Sci. Technol.

Self Cite

178

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“…Product gases from the reactor are sampled at t ¼ 1 hour to determine product formation and TOF values via gas chromatography (GC) (HP 5890, flame ionization (FID) detector) at low conversions (<10%C 2 H 4 conversion). Concentrations and retention times of product gases were determined using calibrated hydrocarbon gas mixtures, propionaldehyde, and standard literature FID sensitivity factors and GC techniques (47,48). Ultrahigh purity (UHP) H 2 was used as received.…”

Section: Methodsmentioning

confidence: 99%

Planar oxide supported rhodium nanoparticles as model catalysts

McClure

Lundwall²,

Goodman³

2010

Proc. Natl. Acad. Sci. U.S.A.

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C 2 H 4 ∕CO∕H 2 reaction is investigated on Rh∕SiO 2 model catalyst surfaces. Kinetic reactivity and infrared spectroscopic measurements are investigated as a function of Rh particle size under near atmospheric reaction conditions. Results show that propionaldehyde turnover frequency (TOF) (CO insertion pathway) exhibits a maximum activity near hd p i ¼ 2.5 nm. Polarization modulation infrared reflection absorption spectroscopy under CO and reaction (C 2 H 4 ∕CO∕H 2 ) conditions indicate the presence of Rh carbonyl species (RhðCOÞ 2 , Rh(CO)H) on small Rh particles, whereas larger particles appear resistant to dispersion and carbonyl formation. Combined these observations suggest the observed particle size dependence for propionaldehyde production via CO insertion is driven by two factors: (i) an increase in propionaldehyde formation on undercoordinated Rh sites and (ii) creation of carbonyl hydride species (Rh(CO)H)) on smaller Rh particles, whose presence correlates with the lower activity for propionaldehyde formation for hd p i < 2.5 nm.Ethylene hydroformylation | CO insertion | polarization modulation infrared reflection absorption spectroscopy | Rh/SiO2 A complicating effect of understanding the structure-activity relationships of heterogeneous catalytic reactions at ambient pressures (near 1 atm or above) is the known ability of reactant gas environments to alter the morphology, particle dispersion, and even the types of adsorbates present on certain supported nanoparticle (NP) systems (1-4). For example, elevated pressure CO ambients have been shown to oxidatively disrupt and disperse Rh nanoparticles, creating highly dispersed gem-dicarbonyl species RhðCOÞ 2 on oxide supports (1-3, 5-8). Under elevated pressure (CO∕H 2 ) and (CO 2 ∕H 2 ) hydrogenation reaction conditions, Rh(CO)H carbonyl hydride species can also be formed (3, 9-12). The creation and stability of such carbonyl species (RhðCOÞ 2 , Rh(CO)H) can depend on particle size, gas pressure, and surface temperature. The cumulative effect of such factors could potentially have an important effect on the overall catalytic properties of the supported Rh NP surface, especially for catalytic reactions involving surface bound CO. Developing an understanding of how such factors can affect the catalytic properties of supported Rh NPs is important from a fundamental surface chemistry perspective. Unraveling these details will require the ability to conduct spectroscopic and kinetic investigations of an informative probe reaction (i) under near atmospheric reaction conditions and (ii) on supported Rh nanoparticles surfaces with well defined initial particle size distributions.CO insertion into adsorbed alkyl groups (R-C x H y ) to form oxygenates (e.g., alcohols, aldehydes) is an important reaction step in many heterogeneous catalytic reactions. For example, C 2 H 4 hydroformylation (C 2 H 4 þ CO þ H 2 ) is a well known reaction for the synthesis of aldehydes via the CO insertion reaction (13). Insightful studies by Chuang and coworkers (14-17) and others (...

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“…The decreases started at lower molecular weights for the more polar aromatics. The largest differences were seen on the analysis with the bench FID instrument (3).…”

Section: Response Of the Fid To Hydrocarbonsmentioning

confidence: 95%