The enthalpies of formation of o-, m-, and p-benzoquinone: gas-phase ion energetics, combustion calorimetry, and quantum chemical computations combined.
Radical anions of o-, m-, and p-benzoquinone were produced in a Fourier transform mass spectrometer by low energy electron attachment or collision-induced dissociation and were differentiated. Classical derivatization experiments also were carried out to authenticate the ortho and meta anions. Gas-phase techniques were used to measure the proton affinities of all three radical anions and the electron affinities of o- and m-benzoquinone. By combining these results in thermodynamic cycles, we derived heats of hydrogenation of o-, m-, and p-benzoquinone (Delta(hyd)H degrees (1o, 1m, and 1p) = 42.8 +/- 4.1, 74.8 +/- 4.1, and 38.5 +/- 3.0 kcal mol(-)(1), respectively) and their heats of formation (Delta(f)H degrees (1o, 1m, and 1p) = -23.1 +/- 4.1, 6.8 +/- 4.1, and -27.7 +/- 3.0 kcal mol(-)(1), respectively). Good accord with the literature value for the para derivative was obtained. Combustion calorimetry and heats of sublimation also were measured for benzil and 3,5-di-tert-butyl-o-benzoquinone. The former heat of formation agreed with previous determinations, while the latter result (Delta(f)H degrees (g) = -73.09 +/- 0.87 kcal mol(-)(1)) was transformed to Delta(f)H degrees (1o) = -18.9 +/- 2.2 kcal mol(-)(1) by removing the effect of the tert-butyl groups via isodesmic reactions. This led to a final value of Delta(f)H degrees (1o) = -21.0 +/- 3.1 kcal mol(-)(1). Additivity was found to work well for m-benzoquinone, but BDE1 and BDE2 for 1,2- and 1,4-dihydroxybenzene differed by a remarkably small 14.1 +/- 4.2 and 23.5 +/- 3.7 kcal mol(-)(1), respectively, indicating that o- and p-benzoquinone should be excellent radical traps.
Fattahi
Alireza
A
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Kass
Steven R
SR
Liebman
Joel F
JF
Matos
M Agostinha R
MA
Miranda
Margarida S
MS
Morais
Victor M F
VM
D016227:Benzoquinones / Q000737:chemistry*; D002151:Calorimetry; D005583:Fourier Analysis; D013058:Mass Spectrometry; D011789:Quantum Theory; D013816:Thermodynamics
D016227:Benzoquinones