Structures, intramolecular rotation barriers, and thermodynamic properties of methane and ethylene carbons bonding to two unsaturated groups : ethylene, acetylene, phenyl and carbonyl
Department of Chemical Engineering, Chemistry and Environmental Science
Master of Science
Bozzelli, Joseph W.
Methane And Ethylene Carbons Bonding
B3LYP/6-31G(d) density functional calculation
Enthalpy, ΔHf°298, entropy, S°298 and heat capacities Cp(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 ΔHf°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 (Cp(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 Cp(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.
njit-etd2001-017 (152 pages ~ 17,694 KB pdf)
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Created November 11, 2002