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Mass Spectrometry: Cycloalkane Fragmentation01:05

Mass Spectrometry: Cycloalkane Fragmentation

1.5K
In mass spectrometry, cycloalkanes exhibit distinct fragmentation patterns due to the inherent stability of their molecular ions compared to linear or branched alkanes. The ring structure of cycloalkanes provides additional stability to the molecular ions, often resulting in prominent ion peaks in the mass spectrum.
For example, cyclohexane molecular ions have a mass-to-charge ratio (m/z) of 84, which tends to produce a stronger signal than linear alkanes like hexane. This stability comes from...
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Halogens03:01

Halogens

19.1K
Group 17 elements, known as halogens, are nonmetals. At room temperature, fluorine and chlorine are gases, bromine is a liquid, and iodine a solid. Astatine is a highly unstable radioactive element, so currently, most of its properties are unknown due to its short half-life. Tennessine is a synthetic element also predicted to be in this group. 
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Mass Spectrometry: Branched Alkane Fragmentation01:29

Mass Spectrometry: Branched Alkane Fragmentation

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This lesson delves into the mass spectrometry of branched alkane fragmentation. Branched alkanes possess secondary or tertiary carbon atoms, which generate relatively stable carbocations if the cleavage occurs at the branching point. The high stability of carbocations drives the instant fragmentation of branched alkanes. Accordingly, the branched alkane's molecular ion peak is very weak or invisible in the mass spectra, especially in comparison to a linear alkane.
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Combustion Energy: A Measure of Stability in Alkanes and Cycloalkanes02:14

Combustion Energy: A Measure of Stability in Alkanes and Cycloalkanes

6.7K
The low reactivity in alkanes can be attributed to the non-polar nature of C–C and C–H σ bonds. Alkanes, therefore, were  initially termed as “paraffins,” derived from the Latin words: parum, meaning “too little,” and affinis, meaning “affinity.”
Alkanes undergo combustion in the presence of excess oxygen and high-temperature conditions to give carbon dioxide and water. A combustion reaction is the energy source in natural gas, liquified...
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Mass Spectrometry: Long-Chain Alkane Fragmentation01:18

Mass Spectrometry: Long-Chain Alkane Fragmentation

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The molecular ions of linear alkanes prefer to fragment at the carbon-carbon bond away from the end of the chain since the cleavage of an inner bond creates a stable carbocation and a stable radical. Consequently, the mass signals of linear alkanes feature intense peaks in the middle of the mass-to-charge ratio plot with weaker peaks on either end. The fragmentation of each carbon-carbon bond with the release of a methyl group in each splitting leads to prominent peaks in the mass spectra...
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Mass Spectrometry: Cycloalkene Fragmentation00:54

Mass Spectrometry: Cycloalkene Fragmentation

1.1K
The molecular ions of cycloalkenes undergo fragmentation via a retro-Diels–Alder reaction.
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Updated: Sep 14, 2025

Identifying Per- and Polyfluorinated Chemical Species with a Combined Targeted and Non-Targeted-Screening High-Resolution Mass Spectrometry Workflow
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Identifying Per- and Polyfluorinated Chemical Species with a Combined Targeted and Non-Targeted-Screening High-Resolution Mass Spectrometry Workflow

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Quantifying the Decomposition Kinetics of Linear C2-C4 Perfluoroalkanes.

Eduardo H Guzman1, Caroline Rocchio1, Keunsoo Kim2

  • 1Department of Chemical and Environmental Engineering, Brown University, Providence, Rhode Island 02906, United States.

The Journal of Physical Chemistry. A
|July 24, 2025
PubMed
Summary

This study investigated the pyrolysis of perfluoroethane (PFE), perfluoropropane (PFP), and perfluorobutane (PFB) using shock tube experiments. The research determined the carbon-carbon bond fission as the primary initiation step for their decomposition.

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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Area of Science:

  • Physical Chemistry
  • Chemical Kinetics
  • Combustion Science

Background:

  • Perfluoroalkanes are important industrial chemicals with complex decomposition pathways.
  • Understanding their pyrolysis is crucial for predicting combustion behavior and environmental fate.
  • Previous studies often lacked detailed kinetic data for C2-C4 perfluoroalkanes.

Purpose of the Study:

  • To investigate the pyrolysis mechanisms of linear perfluoroalkanes (C2-C4).
  • To determine the unimolecular decomposition rate constants for perfluoroethane (PFE), perfluoropropane (PFP), and perfluorobutane (PFB).
  • To develop a detailed chemical kinetic model for perfluoroalkane pyrolysis.

Main Methods:

  • Laser schlieren densitometry (LS) in a diaphragmless shock tube.
  • Shock-heating of perfluoroalkane/krypton mixtures to 1400-2500 K.
  • Analysis of density gradient profiles to infer kinetic parameters.

Main Results:

  • Carbon-carbon bond fission was identified as the initiation step for all perfluoroalkanes.
  • Perfluoroethane and perfluoropropane exhibited one primary dissociation channel.
  • Perfluorobutane showed two competing carbon-carbon bond-fission pathways.
  • Computed rate constants were integrated into a comprehensive kinetic model.

Conclusions:

  • The developed kinetic model accurately simulates the pyrolysis of C2-C4 perfluoroalkanes.
  • The study provides critical kinetic data for understanding perfluoroalkane decomposition.
  • Findings contribute to improved predictive models for combustion and high-temperature chemistry.