Chromatogram simulation by area reproduction

Bøe, Bjarne

doi:10.1016/j.chroma.2006.11.013

Cited by 5 publications

(7 citation statements)

References 7 publications

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“…For ease of visual comparison between theory and experiment we adopt the device of plotting experimental chromatographic data alongside fitted theoretical curves of major products. The chromatographic peaks modeled tend to be rather asymmetric; chromatograms have therefore been simulated with modified Poisson functions of the form given in eq : h ( t ) = h max normale − k ( t − t r ) [ 1 + k n false( t − t normalr false) ] n …”

Section: Theoretical Resultsmentioning

confidence: 99%

“…The retention time of the fitted peak is given by t r , h max is the peak height, and k and n are Poisson model parameters. The parameters t r , k , and n are derived exclusively from the shapes and positions of the experimental peaks . Thereafter, the peak height parameter h max , is dictated solely by the predicted relative product yields from our model.…”

Section: Theoretical Resultsmentioning

confidence: 99%

“…The parameters t r , k, and n are derived exclusively from the shapes and positions of the experimental peaks. 105 Thereafter, the peak height parameter h max , is dictated solely by the predicted relative product yields from our model. Integration of eq 7 yields…”

Section: A E E E Aementioning

confidence: 96%

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Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

McIntosh

Russell

2014

J. Phys. Chem. A

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This work presents a study of the pyrolytic formation of vinylacetylene and benzene congeners formed from chlorinated hydrocarbon precursors, a complex, multipath polymerization system formed in a monomer-rich environment. (Co-)pyrolyses of dichloro- and trichloroethylene yield a rich array of products, and assuming a single dominant underlying growth mechanism, this (on comparing expected and observed products) allows a number of potentially competing channels to C4 and C6 products to be ruled out. Poor congener/isomer descriptions rule out even-carbon radical routes, and the absence of C3 and C5 products rule out odd-carbon processes. Vinylidenes appear unable to describe the increased reactivity of acetylenes with chlorination noted in our experiments, leaving molecular acetylene dimerization processes and, in C6 systems, the closely related Diels-Alder cyclization as the likely reaction mechanism. The feasibility of these routes is further supported by ab initio calculations. However, some of the most persuasive evidence is provided by congener-specific yield predictions enabled by the construction of a probability tree analogue of kinetic modeling. This approach is relatively quick to construct, provides surprisingly accurate predictions, and may be a very useful tool in screening for important reaction channels in poorly understood congener- or isomer-rich reaction systems.

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Section: Theoretical Resultsmentioning

confidence: 99%

Section: Theoretical Resultsmentioning

confidence: 99%

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Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

McIntosh

Russell

2014

J. Phys. Chem. A

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show abstract

“…For easy visual comparison between theory and experiment, we adopt the device of plotting experimental chromatographic data alongside fitted theoretical curves of major products. The chromatographic peaks modeled tend to be rather asymmetric; chromatograms have therefore been simulated with modified Poisson functions of the form given in eq : h ( t ) = h max normale prefix− k ( t − t r ) [ 1 + k n false( t − t normalr false) ] n …”

Section: Experimental and Computational Methodologymentioning

confidence: 99%

“…The parameters t r , k, and n are derived exclusively from the shapes and positions of the experimental peaks. 75 Thereafter, the peak height parameter h max is dictated solely by the predicted relative product yields from our model. Integration of eq 5 yields eq 6.…”

Section: ■ Introductionmentioning

confidence: 99%

Role of Hydrogen Abstraction Acetylene Addition Mechanisms in the Formation of Chlorinated Naphthalenes. 2. Kinetic Modeling and the Detailed Mechanism of Ring Closure

McIntosh

Russell

2014

J. Phys. Chem. A

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The dominant formation mechanisms of chlorinated phenylacetylenes, naphthalenes, and phenylvinylacetylenes in relatively low pressure and temperature (∼40 Torr and 1000 K) pyrolysis systems are explored. Mechanism elucidation is achieved through a combination of theoretical and experimental techniques, the former employing a novel simplification of kinetic modeling which utilizes rate constants in a probabilistic framework. Contemporary formation schemes of the compounds of interest generally require successive additions of acetylene to phenyl radicals. As such, infrared laser powered homogeneous pyrolyses of dichloro- or trichloroethylene were perturbed with 1,2,4- or 1,2,3-trichlorobenzene. The resulting changes in product identities were compared with the major products expected from conventional pathways, aided by the results of our previous computational work. This analysis suggests that a Bittner-Howard growth mechanism, with a novel amendment to the conventional scheme made just prior to ring closure, describes the major products well. Expected products from a number of other potentially operative channels are shown to be incongruent with experiment, further supporting the role of Bittner-Howard channels as the unique pathway to naphthalene growth. A simple quantitative analysis which performs very well is achieved by considering the reaction scheme as a probability tree, with relative rate constants being cast as branching probabilities. This analysis describes all chlorinated phenylacetylene, naphthalene, and phenylvinylacetylene congeners. The scheme is then tested in a more general system, i.e., not enforcing a hydrogen abstraction/acetylene addition mechanism, by pyrolyzing mixtures of di- and trichloroethylene without the addition of an aromatic precursor. The model indicates that these mechanisms are still likely to be operative.

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Computational fluid dynamic simulation of axial and radial flow membrane chromatography: Mechanisms of non-ideality and validation of the zonal rate model

Ghosh

Vahedipour

Lin

et al. 2013

Journal of Chromatography A

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Chromatogram simulation by area reproduction

Cited by 5 publications

References 7 publications

Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

Role of Hydrogen Abstraction Acetylene Addition Mechanisms in the Formation of Chlorinated Naphthalenes. 2. Kinetic Modeling and the Detailed Mechanism of Ring Closure

Computational fluid dynamic simulation of axial and radial flow membrane chromatography: Mechanisms of non-ideality and validation of the zonal rate model

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Chromatogram simulation by area reproduction

Cited by 5 publications

References 7 publications

Experimental and Theoretical Studies into the Formation of C4–C6 Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

Experimental and Theoretical Studies into the Formation of C4–C6 Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

Role of Hydrogen Abstraction Acetylene Addition Mechanisms in the Formation of Chlorinated Naphthalenes. 2. Kinetic Modeling and the Detailed Mechanism of Ring Closure

Computational fluid dynamic simulation of axial and radial flow membrane chromatography: Mechanisms of non-ideality and validation of the zonal rate model

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Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions