Heat of formation of phenyl benzoate and related bond dissociation energies

1967 ◽  
pp. 720 ◽  
Author(s):  
G. P. Adams ◽  
D. H. Fine ◽  
Peter Gray ◽  
P. G. Laye
Keyword(s):  
Heat Of Formation ◽  
Bond Dissociation Energies ◽  
Phenyl Benzoate ◽  
Bond Dissociation ◽  
Dissociation Energies

A study of the C 2 H 4 +HCl=C 2 H 5 Cl and C 2 H 4 +HBr=C 2 H 5 Br equilibria

1953 ◽  
Vol 216 (1126) ◽  
pp. 361-374 ◽  
Keyword(s):  
Equilibrium Constants ◽  
Entropy Change ◽  
Heat Of Formation ◽  
Ethyl Chloride ◽  
Ethyl Bromide ◽  
Bond Dissociation Energies ◽  
Kcal Mole ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Heat Of Dissociation

The equilibrium constants of the two reactions C 2 H 4 + H X = C 2 H 5 X , where X = Cl or Br, have been measured for X = Cl from 449 to 491° K, and for X = Br from 515 to 573° K, The methods of preparing and purifying the substances used, of carrying out the analyses and of determining the equilibrium constants have been described. The results for the ethyl chloride equilibrium were combined with calculations of the entropy change using Gordon & Giauque’s barrier height in ethyl chloride of 3700 cal/mole to obtain a value for the heat content change. The value for this, corrected to 298° K, is 17·1 kcal/mole. This leads to a heat of formation of ethyl chloride of – 26·7 and a heat of dissociation of the C—Cl bond in ethyl chloride of 80·9 kcal/mole. For the ethyl bromide equilibrium, the entropy change was calculated using barrier heights in ethyl bromide of 3000, 4000 and 5000 cal/mole. Using the entropy changes calculated it was concluded that the heat of reaction, corrected to 298° K, is within 0·3 kcal/mole of 19·1. This leads to a heat of formation of ethyl bromide of – 15·3 and a heat of dissociation of the C—Br bond in ethyl bromide of 67·2 kcal/mole. The two bond dissociation energies have been incorporated in the recent tables of Mortimer, Pritchard & Skinner listing such energies. The significance of the values for the bond dissociation energies in the series of RX molecules, where R = Me, Et, n-Pr, n-Bu, iso-Pr and tert.-Bu , and X = H, Cl and Br have been discussed.

Electron-impact study of some binary metal carbonyls

1967 ◽  
Vol 45 (6) ◽  
pp. 641-648 ◽  
Author(s):  
D. R. Bidinosti ◽  
N. S. McIntyre
Keyword(s):  
Mass Spectra ◽  
Major Ions ◽  
Heat Of Formation ◽  
Bond Dissociation Energies ◽  
Metal Carbonyls ◽  
Kcal Mole ◽  
Carbon Bond ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
The Mean

The mass spectra and appearance potentials for the major ions from Ni(CO)4, Fe(CO)5, Cr(CO)6, Mo(CO)6, W(CO)6, and V(CO)6 have been measured. Heats of formation have been calculated for 39 ions of the type M(CO)n+, where M = Ni, Fe, Cr, Mo, W, and V. The mean metal–carbon bond dissociation energies have been calculated for both the neutral molecules and the parent ions. From a comparison with the available thermochemical data for the neutral molecules it is concluded that the mean vanadium–carbon bond dissociation energy is 28 kcal/mole and the heat of formation of V(CO)6 vapor is − 204 kcal/mole.

The pyrolysis of benzoyl bromide and the determination of the relevant bond dissociation energies

1952 ◽  
Vol 214 (1117) ◽  
pp. 273-280 ◽  
Keyword(s):  
Least Square Method ◽  
Heat Of Formation ◽  
Least Square ◽  
Bond Dissociation Energies ◽  
Kcal Mole ◽  
Bond Dissociation ◽  
Rapid Decomposition ◽  
Dissociation Energies ◽  
Rate Determining Step

Pyrolysis of benzoyl bromide in the presence of excess of toluene has been investigated. It has been shown that the rate-determining step is the unimolecular dissociation C 6 H 5 . CO. Br → C 6 H 5 . CO + Br, followed by the rapid decomposition of benzoyl radicals C 6 H 5 . CO → C 6 H 5 ⋅ + CO. Bromine atoms and phenyl radicals seem to be removed from the system by the reactions C 6 H 5 . CH 3 + Br → C 6 H 5 . CH 2 ⋅ + HBr and C 6 H 5 . CH 3 + Ph ⋅→ C 6 H 5 . CH 2 ⋅ + C 6 H 6 . The activation energy of the rate-determining dissociation process has been estimated using the least square method at 57⋅0 kcal/mole and has been identified with D (C 6 H 5 ⋅ CO-Br). Thus, having D (C 6 H 5 ⋅ CO-Br) = 57⋅0 kcal/mole, the heat of formation of benzoyl radicals has been calculated at ∆ H f (C 6 H 5 . CO) = 15⋅6 kcal/mole, and consequently the values for various bond dissociation energies of the type D (C 6 H 5 . CO- X ) have been derived.

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