Determination of ΔHf2980(C6F5I,g) from Studies of the Combustion of Iodopentafluorobenzene in Oxygen and Calculation of D(C6F5—X) Bond Dissociation Energies

1974 ◽  
Vol 52 (15) ◽  
pp. 2673-2678 ◽  
Author(s):  
Michael J. Krech ◽  
Stanley James W. Price ◽  
Wayne F. Yared
Keyword(s):  
Material Balance ◽  
Combustion Method ◽  
Heat Of Formation ◽  
Molar Ratio ◽  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Direct Combustion ◽  
Tenfold Excess

The heat of formation of iodopentafluorobenzene has been determined using the direct combustion method previously developed and used for hexafluorobenzene and octafluorotoluene. The combustion with oxygen yields CO2, CF4, F2, I2, and IF5. With a tenfold excess of oxygen the average CO2 to CF4 molar ratio is 11.08 ± 0.028. A material balance was obtained for carbon and fluorine. An apparent shortfall of about 30% in iodine has been related to the formation of IO2(OH) during analysis. The value of ΔHf2980 (C6F5I,g) = −133.2 ± 3.0 kcal mol−1 has been combined with D(C6F5—I) and ΔHf2980(I, g) to obtain ΔHf2980(C6F5,g) = −92.6 kcal mol−1 Using this value and the appropriate values of ΔHf2980 (C6F5X,g) and ΔHf2980(X, g), values of D(C6F5—X) have been calculated for X = OH, H, F, Cl, I, CH3, and CF3.

Determination of ΔHf2980(C6F5Br, g) from studies of the combustion of bromopentafluorobenzene in oxygen and calculation of D[C6F5 — Br]

1977 ◽  
Vol 55 (24) ◽  
pp. 4222-4226 ◽  
Author(s):  
Michael J. Krech ◽  
Stanley James W. Price ◽  
Henry J. Sapiano
Keyword(s):  
Material Balance ◽  
Combustion Method ◽  
Heat Of Formation ◽  
Molar Ratio ◽  
Direct Combustion ◽  
A Value ◽  
Fold Excess

The heat of formation of bromopentafluorobenzene has been determined through the use of the direct combustion method which has been applied to hexafluorobenzene, octafluorotoluene, and iodopentafluorobenzene. While a platinum lined bomb is normally used for these types of compounds a steel bomb had to be adopted in this work. The combustion of bromopentafluorobenzene in the steel bomb yields CO2, CF4, F2, Br2, and BrF3. With a ten-fold excess of oxygen, the average CO2 to CF4 molar ratio is 7.29 ± 0.07. A material balance was obtained for carbon, fluorine, and bromine. The value of ΔHf2980(C6F5Br, g) = −711.6 ± 16.7 kJ mol−1 (−170.1 ± 4.0 kcal mol−1) has been combined with ΔHf2980(C6F5, g) = −387.4 kJ mol−1 (−92.6 kcal mol−1) and ΔHf2980(Br, g) = 111.7 kJ mol−1 (26.7 kcal mol−1) to obtain a value for D[C6F5—Br] of 435.9 kJ mol−1 (104.2 kcal mol−1).

Determination of the Heat of Formation of Octafluorotoluene and Calculation of D[C6F5—F] – D[C6F5—CF3]

1973 ◽  
Vol 51 (22) ◽  
pp. 3662-3664 ◽  
Author(s):  
Michael J. Krech ◽  
Stanley James W. Price ◽  
Wayne F. Yared
Keyword(s):  
Material Balance ◽  
Combustion Method ◽  
Heat Of Formation ◽  
Enthalpies Of Formation ◽  
Direct Combustion ◽  
Fold Excess

The heat of formation of octafluorotoluene has been determined using the direct combustion method previously developed for hexafluorobenzene. As in the hexafluorobenzene case the combustion of octafluorotoluene in oxygen yields CO2, CF4, and F2. With a ten-fold excess of oxygen the CO2 to CF4 ratio is 3.85 ± 0.06. A full material balance was obtained. The value of ΔHf2980(C6F5CF3,g) = −303.2 ± 1.8 kcal mol−1 may be combined with the enthalpies of formation of C6F6, CF3, and F to give D[C6F5—F] – D[C6F5—CF3] = 55.7 ± 4.0 kcal mol−1.

scholarly journals Determination of ΔHf2980(C12F10,g) from studies of the combustion of decafluorobiphenyl in oxygen and calculation of D(C6F5—C6F5)

1979 ◽  
Vol 57 (12) ◽  
pp. 1468-1470 ◽  
Author(s):  
Stanley James W. Price ◽  
Henry J. Sapiano
Keyword(s):  
Material Balance ◽  
Combustion Method ◽  
Heat Of Formation ◽  
Direct Combustion ◽  
Related Compounds ◽  
Fold Excess

The heat of formation of decafluorobiphenyl has been determined by the direct combustion method previously developed and used for hexafluorobenzene and related compounds. As in the hexafluorobenzene case the combustion of decafluorobiphenyl in oxygen yields CO2, CF4, and F2. With a ten-fold excess of oxygen the CO2 to CF4 ratio is 5.85 ± 0.08. A full material balance was obtained. The value of ΔHf2980(C12F10,g) = −1263.2 ± 5.1 kJ mol−1 may be combined with ΔHf2980(C6F5,g) = −387.4 ± 12.0 kJ mol−1 to give D(C6F5—C6F5) = 488.4 ± 24.5 kJ mol−1. Also with ΔHf2980(C6F6,g) = −945.6 ± 8.0 kJ mol−1 ΔH2980 for reaction [3][Formula: see text]is calculated to be −628.0 ± 16.8 kJ mol−1.

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.

Experimental methods for measurement of bond dissociation energies and heats of formation of radicals

1951 ◽  
Vol 207 (1088) ◽  
pp. 5-13 ◽  
Keyword(s):  
Experimental Methods ◽  
Experimental Results ◽  
Heats Of Formation ◽  
Bond Dissociation Energies ◽  
Carrier Gas ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Kinetics Of

The paper describes a pyrolytic method of investigating the kinetics of gaseous reactions in which toluene is used as a carrier gas. It is shown that the method is particularly suitable for the determination of bond dissociation energies. The scope of the method is illustrated by various examples. A list of bond dissociation energies obtained is given. The manner in which the experimental results obtained can be cross-checked, is indicated and illustrated by examples. The effects of various constitutional factors on the bond dissociation energies are discussed.

Sign in / Sign up

Export Citation Format

Share Document