Structures, intramolecular rotation barriers, and thermodynamic properties of methane and ethylene carbons bonding to two unsaturated groups : ethylene, acetylene, phenyl and carbonyl

Author

Manish H. Gurbani, New Jersey Institute of Technology

Document Type

Thesis

Date of Award

Spring 5-31-2001

Degree Name

Master of Science in Chemical Engineering - (M.S.)

Department

Chemical Engineering, Chemistry and Environmental Science

First Advisor

Joseph W. Bozzelli

Second Advisor

Robert Pfeffer

Third Advisor

Basil Baltzis

Abstract

Enthalpy, ΔH_f°₂₉₈, entropy, S°₂₉₈ and heat capacities C_p(T) (300 ≤ T/K ≤ 1500) are determined for Methane, bi-phenyl (CCB2H2); Methane, phenyl-vinyl (CCBCDH2);Toluene, 1-formyl (CCBCOH2), Propyne, 3-phenyl (CCBCTH2); 1,4-pentadiene (CCD2H2); Propene, 3-formyl (CCDCOH2); Methane, di-formyl (CCO2H2); Propyne, 3-formyl (CCOCTH2); Methane, di-ethynl (CCT2H2); Ethene, bi-phenyl (CDCB2); 1,4 Butadiene, 3-phenyl (CDCBCD); Ethene, I-ethynl-l-phenyl (CDCBCT); 1,4 Butadiene,3-vinyl (CDCD2); 1,4 Butadiene, 2-ethynl (CDCDCT) and Ethene, 1,1di-ethynl(CDCT2) using density functional B3LYP/6-31G(d) calculation method. Molecular structures and vibration frequencies are determined at the B3LYP/6-31G(d) density functional calculation level. Evaluation of data from the isodesmic reactions results in ΔH_f°₂₉₈ values for CCB2H2 of 42.41 kcal/mol, CCBCDH2 of 34.7 kcal/mol, CCBCOH2 of -13.35 kcal/mol, CCBCTH2 of 74.7 kcal/mol, CCD2H2 of 27.08 kcal/mol, CCDCOH2 of -20.68 kcal/mol, CCO2H2 of -64.88 kcal/mol, CCOCTH2 of 19.72 kcal/mol, CCT2H2 of 112.43 kcal/mol, CDCB2 of 60.86 kcal/mol, CDCBCD of 53.41kcal/mol, CDCBCT of 94.96 kcal/mol, CDCD2 of 48.68 kcal/mol, CDCDCT of 85.45 kcal/mol and CDCT2 of 131.68 kcal/mol. Standard entropy (S°₂₉₈) and heat capacity (C_p(T)'s, 300 ≤ T/K ≤ 1500) from vibrational, translational, and external rotational contributions are calculated using the rigid-rotor-harmonic-oscillator approximation based on the vibration frequencies and structures obtained from the density functional studies. Potential energy as a function of internal rotation barrier is also determined using relaxed and non relaxed calculations using the B3LYP functional. Hindered internal rotational contributions to Entropy and Heat Capacity are calculated by the method of Pitzer and Gwinn. Groups for use in Benson type additivity estimations are determined. Enthalpy, entropy and C_p(T) properties are determined for C/CB2/H2, C/CB/CD/H2, C/CB/CO/H2, C/CB/CT/H2, C/CD2/H2, C/CD/CO/H2, C/CO2/H2, C/CO/CT/H2, C/CT2/H2, CD/CB2, CD/CB/CD, CD/CB/CT, CD/CD2, CD/CD/CT, CD/CT2 groups for use in group additivity. Calculations result Group Values for C/CB2/H2 of -1.61 kcal/mol, C/CB/CD/H2 of -2.16 kcal/mol, C/CB/CO/H2 of -5.96 kcal/mol, C/CB/CT/H2 of -1.81kcal/mol, C/CD2/H2 of -2.62 kcal/mol, C/CD/CO/H2 of -6.13 kcal/mol, C/CO2/H2 of -6.08 kcal/mol, C/CO/CT/H2 of -5.38 kcal/mol, C/CT2/H2 of -3.43 kcal/mol, CD/CB2 of 10 kcal/mol, CD/CB/CD of 11.81 kcal/mol, CD/CB/CT of 11.3 kcal/mol, CD/CD2 of 12.19, CD/CD/CT of 11.05 kcal/mol, CD/CT2 of 15.22 kcal/mol.

Recommended Citation

Gurbani, Manish H., "Structures, intramolecular rotation barriers, and thermodynamic properties of methane and ethylene carbons bonding to two unsaturated groups : ethylene, acetylene, phenyl and carbonyl" (2001). Theses. 734.
https://digitalcommons.njit.edu/theses/734