Computational Studies on the Thermodynamic and Kinetic Parameters of Unimolecular and Bimolecular Dissociation of Propylene Glycol Ethyl Ether in Binary 1-Butanol and Isobutanol Solvent Mixtures

Al Omari, Rima H.; Al Azzam, Khaldun M.; Almatarneh, Mansour H.; Ahmad, Ahmad A.; Ghazzya, Asma M.; Alnajajrahb, Asmaa Y.; Shalan, Naeem M.; Karameh, Nida O.; Bekbayeva, Lyazzat; Negim, El-Sayed Moussa

doi:10.21608/ejchem.2022.121471.5448

Computational Studies on the Thermodynamic and Kinetic Parameters of Unimolecular and Bimolecular Dissociation of Propylene Glycol Ethyl Ether in Binary 1-Butanol and Isobutanol Solvent Mixtures

Document Type : Original Article

Authors

¹ Pharmacological and Diagnostic Research Center (PDRC), Department of Pharmaceutical Sciences, Faculty of Pharmacy, Al-Ahliyya Amman University, Amman 19328, Jordan

² Department of Chemistry, University of Jordan, Amman 11942, Jordan. Department of Chemistry, Memorial University, St. John’s, NL, A1B 3X7, Canada

³ Department of Applied Physics, Faculty of Science and Arts, Jordan University of Science and Technology, Irbid-22110, Jordan.

⁴ Pharmacological and Diagnostic Research Centre (PDRC), Faculty of Pharmacy, Al-Ahliyya Amman University, Amman 19328, Jordan.

⁵ Department of Chemistry, University of Jordan, Amman 11942, Jordan.

⁶ Asfendiyarov Kazakh National Medical University, Department of Engineering disciplines, 88 Tole bi St., Almaty, Kazakhstan

⁷ School of Petroleum Engineering, Satbayev University, 22 Satpayev Street, 050013 Almaty, Kazakhstan

10.21608/ejchem.2022.121471.5448

Abstract

This study includes a theoretical investigation of Thermodynamic and kinetics of the unimolecular and bimolecular dissociation reaction of Propylene Glycol Ethyl Ether in the gaseous phase. A B3LYP functional with 6-31G(d) basis set was used to optimize all geometries of the stationary points. Potential-energy surface for various channels for the reaction of PGEE was studied at APFD/6-31G(d) and ωB97XD/6-31G(d) levels of theory. The kinetic and thermodynamic parameters for nineteen reaction pathways are investigated. Most of the unimolecular dissociation mechanisms occur in a concerted transition state step endothermically. Our calculations proved that energy barriers for ethanol and acetone formation is the best reaction route with an activation barrier of 279 kJ mol-1 at APFD/6-31G(d) level of theory. The PGEE bimolecular reaction with 1-butanol, the pathway which produces H2 and butanal is more plausible to take place with a lower activation energy of 225 kJ mol-1 at ωB97XD/6-31G(d) level of theory.

Keywords