Thermodynamic properties of chlorocarbons and kinetic analysis for a- and b -addition of OH+C2H3CL

Author

Li Zhu, New Jersey Institute of Technology

Document Type

Thesis

Date of Award

Fall 1-31-1998

Degree Name

Master of Science in Applied Chemistry - (M.S.)

Department

Chemical Engineering, Chemistry and Environmental Science

First Advisor

Joseph W. Bozzelli

Second Advisor

Carol A. Venanzi

Third Advisor

Barbara B. Kebbekus

Abstract

Thermodynamic properties, ΔHf°₂₉₈, S°₂₉₈ and Cp(T) 300≤T/K≤1500, for C₁, C₂ chlorocarbons are calculated by AM1 and PM3 in MOPAC6, then compared with the literature data. AM1- and PM3-derived S°298 and Cp(T) (300≤T/K≤1500) are found to be consistent with the literature (Rd ≤ ± 5%). ΔHf°₂₉₈ of CH₂Cl₂, CH₂ClCH₂Cl, CH₂ClCHCl₂, CHCl₂CHCl₂, and C₂Cl₄ and C₂Cl₂ calculated by PM3 as well as ΔHf°₂₉₈ of CCl₄, C₂HCl₃, C₂Cl₄ and C₂Cl₂ by AM1 have more than ± 5 kcal/mol deviations. A Modified Group Additivity method is shown to be precise when compared with the literature.

A complete reaction system consisting of 12 elementary reaction and 19 species has been developed to model the reaction system of OH + C₂H₃Cl. There are two different carbon sites where addition can occur, α-addition and β-addition, as well as two different abstractions, α-abstraction and β-abstraction. Thermochemical kinetic parameters are developed for each elementary reaction and a chemical activation kinetic analysis using Multi-frequency QRRK theory for k(E) and modified strong collision approach for fall-off is used to calculate k's as function of pressure and temperature. Thermodynamic parameters are determined by MOPAC6/PM3 and the Group Additivity estimation. We are trying to use ab initio and density function methods at different levels to calculate the addition reactants, products and the transition states. All reactions in the mechanism incorporate reverse reaction rates calculated from thermodynamic parameters and Microscopic Reversibility. Results show good agreement with several experimental data. Recommended rate constants for the primary addition channels at 760 torr are: k(OH + C₂H₃Cl --> CH₂OHC.HCl) = 4.22x10³⁰ x T^-5.88e^4837/RT cm³mol^-1sec^-1k(OH + C₂H₃Cl --> Cl + CH₂CHOH) = 8.61x10¹² x T^0.01e^4114/RT cm³mol^-1sec^-1.

Recommended Citation

Zhu, Li, "Thermodynamic properties of chlorocarbons and kinetic analysis for a- and b -addition of OH+C2H3CL" (1998). Theses. 972.
https://digitalcommons.njit.edu/theses/972