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Kinetics and thermodynamics of unimolecular dissociation of n-C3H7I

  • Nikita Bystrov , Alexander Emelianov , Alexander Eremin and Pavel Yatsenko ORCID logo EMAIL logo
Published/Copyright: January 25, 2024
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 238 Issue 7

Abstract

The present work expands previous studies on the kinetics of the n-C3H7I unimolecular decomposition and the thermodynamic properties of n-C3H7I and i-C3H7I molecules, by providing combined experimental and theoretical data on the rate constant for reaction of n-C3H7I + Ar ⇌ n-C3H7 + I + Ar, as well as thermodynamic data for iodopropane isomers, calculated based on the density functional theory. The n-C3H7I dissociation rate constant has been precisely determined in shock-tube experiments by applying atomic resonance absorption spectrometry (ARAS) at the resonance transition wavelength of atomic iodine (183.0 nm) in a temperature range from 830 to 1230 K at a pressure of 3–4 bar. The resulting expression is presented in the Arrhenius form: k1st = 1.17 × 1013exp(−191.4 kJ mol−1/RT) (s−1). Theoretical RRKM/ME calculation of the temperature- and pressure-dependent rate constant and channel branching ratio have been based on quantum chemical calculations and were performed over a wide range of thermodynamic conditions (T = 300–2000 K, p = 10−4 to 102 bar). Additionally, the thermochemistry of the reactions of n-C3H7I dissociation and isomerization has been calculated on B3LYP/cc-pVTZ-PP level of theory. Thermodynamic data, which are provided in NASA polynomial format, are in a better agreement with the available experimental data and previous theoretical estimates.

Keywords: iodopropane; dissociation rate constant; shock tube; atomic resonance absorption spectrometry (ARAS); RRKM/ME
Corresponding author: Pavel Yatsenko, Joint Institute for High Temperatures of the Russian Academy of Sciences, Izhorskaya 13 Bldg. 2, Moscow 125412, Russia, E-mail:

Acknowledgments

The authors express their deep gratitude to Professor Alexander Mebel (Florida International University) for valuable comments and help in mastering theoretical calculations.

  1. Research ethics: Not applicable.

  2. Author contributions: The authors have accepted responsibility for the entire content of this manuscript and approved submission.

  3. Competing interests: The authors state no conflict of interest.

  4. Research funding: None declared.

  5. Data availability: The raw data can be obtained on request fron the corresponding author.

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Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/zpch-2023-0385).

Received: 2023-10-10
Accepted: 2024-01-03
Published Online: 2024-01-25
Published in Print: 2024-07-26

© 2024 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.1515/zpch-2023-0385
Keywords for this article
iodopropane; dissociation rate constant; shock tube; atomic resonance absorption spectrometry (ARAS); RRKM/ME

Articles in the same Issue

  1. Frontmatter
  2. Review Articles
  3. Synthetic methodologies to access bioactive bis-coumarin scaffold: a recent progress
  4. Removal of CO in flue gas by catalytic oxidation: a review
  5. Original Papers
  6. Adsorption and visible light driven photocatalytic degradation of Malachite Green and Methylene Blue dye in wastewater using magnetized copper metal organic framework
  7. Removal of chemicals from effluent using photobioreactor technology to improve environmental and health impacts
  8. Kinetics and thermodynamics of unimolecular dissociation of n-C3H7I
  9. Microwave-accelerated heating technique in fabrication of silver nanoparticles using propolis extract: optimization and characterization
  10. In vitro study on the inflammatory response of chitosan nanoparticles as a potential siRNA carrier targeting towards osteosarcoma cells
  11. Formulation and development of topical iron oxide nanoemulgel using Punica granatum extract and in vitro evaluation of anti-inflammatory potential in rheumatoid arthritis
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