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.

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 ΔH0f298(C6F10,g) and ΔH0f298(C6F12,g) from studies of the combustion of decafluorocyclohexene and dodecafluorocyclohexane in oxygen and calculation of the resonance energy of hexafluorobenzene

1979 ◽  
Vol 57 (6) ◽  
pp. 685-688 ◽  
Author(s):  
Stanley James W. Price ◽  
Henry J. Sapiano
Keyword(s):  
Material Balance ◽  
Resonance Energy ◽  
Combustion Method ◽  
Heats Of Formation ◽  
Reaction Products ◽  
Molar Ratios ◽  
Direct Combustion ◽  
Related Compounds ◽  
Fold Excess

The heats of formation of decafluorocyclohexene and dodecafluorocyclohexane have been determined by the direct combustion method previously developed and used for hexafluorobenzene and related compounds. The combustion of decafluorocyclohexene and dodecafluorocyclohexane formed the reaction products CO2, CF4, and F2. In both cases a portion of the compound remained unburned. The unburned material was collected and quantitatively determined gravimetrically. A material balance was obtained for carbon and fluorine on the basis of CO2, CF4, and F2 and the amount of unburned compound. With a ten-fold excess of oxygen, the average CO2-to-CF4 molar ratios for C6F10 and C6F12 are 2.03 ± 0.01 and 1.35 ± 0.01, respectively. The values obtained for the heats of formation are ΔH0f298(C6F10,g) = −1906.6 ± 7.2 kJ mol−1 and ΔH0f298(C6F12,g) = −2368.9 ± 7.6 kJ mol−1. ΔH0f298 for the reaction C6F10(g) + F2(g) → C6F12(g) was calculated to be −462.3 ± 14.8 kJ mol−1 and the 'resonance energy' of C6F6 is estimated at −36.4 kJ mol−1.

Determination of the Heat of Formation of Hexafluorobenzene

1972 ◽  
Vol 50 (18) ◽  
pp. 2935-2938 ◽  
Author(s):  
M. Krech ◽  
S. J. W. Price ◽  
W. F. Yared
Keyword(s):  
Aromatic Compounds ◽  
Visual Inspection ◽  
Material Balance ◽  
Heat Of Formation ◽  
Heat Of Combustion ◽  
New Method ◽  
Complete Combustion ◽  
Auxiliary Substance ◽  
Hydrocarbon Oil

A new method has been developed for determining the heat of combustion of perfluoro aromatic compounds. The basic differences from previous methods are that no auxiliary substance is used and no water is present in the bomb. The combustion of hexafluorobenzene in a platinum lined bomb yields CO2, CF4, and F2. Visual inspection and the material balance indicate that complete combustion is obtained. The value of [Formula: see text] obtained by this method is −224.0 ± 2.0 kcal/mol. Recalculation of the result of Cox etal. (1, 2) obtained from combustion of C6F6 in mylar bags in the presence of hydrocarbon oil and water leads to[Formula: see text]

Determination of D[C6F5CH2—Br] by the toluene carrier method

1980 ◽  
Vol 58 (18) ◽  
pp. 1906-1908 ◽  
Author(s):  
R. John Kominar ◽  
Michael J. Krech ◽  
Stanley James W. Price
Keyword(s):  
Arrhenius Equation ◽  
Parent Compound ◽  
Material Balance ◽  
Internal Standard ◽  
Standard Technique ◽  
The Other ◽  
Reasonable Estimate ◽  
First Order ◽  
A Value

The pyrolysis of C6F5CH2Br has been studied by the toluene carrier technique over the temperature range 727–800 °C. Rate constants are based on analysis for residual parent compound by gas chromatography using an internal standard technique. In selected runs a material balance of 100 ± 2% was obtained for bromine based on C6F5CH2Br plus HBr. Within the limits of the experimental technique the process appears to be first order and homogeneous. In addition to HBr the other major products of the thermal decomposition are C6F5CH3, (C6F5CH2)2, C6F5CH2CH2C6H5, and (C6H5CH2)2. The Arrhenius equation obtained is[Formula: see text]The log A value is very close to the value of 14.6 recommended by Benson and O'Neal for the decomposition of C6H5CH2Br. The activation energy, 225 ± 6 kJ mol−1, should be a reasonable estimate of D[C6F5CH2—Br].

Optical Purity Determination and 1H NMR Spectral Simplification with Lanthanide Shift Reagents. II. Thiamylal, 5-Allyl-5-(1-methylbutyl)-2-thiobarbituric Acid

1984 ◽  
Vol 38 (1) ◽  
pp. 74-78 ◽  
Author(s):  
S. Eberhart ◽  
R. Rothchild
Keyword(s):  
Optical Purity ◽  
Thiobarbituric Acid ◽  
Carbonyl Oxygen ◽  
Shift Reagent ◽  
Coupling Constants ◽  
Molar Ratio ◽  
Line Broadening ◽  
A Value ◽  
Purity Evaluation

A racemic sample of thiamylal, 5-allyl-5-(1-methylbutyl)-2-thiobarbituric acid, 1, has been shown to exhibit significant enantiomeric shift differences, ΔΔδ, for the CH3- CH proton absorptions when treated with the chiral lanthanide shift reagent, tris[3-(trifluoromethylhydroxy-methylene)- d-camphorato| europium (III), 2, in CDC13 at 28°. For example, at the relatively low molar ratio of 2:1 of 0.181, a value of ΔΔδ of 22 Hz (0.36δ) was observed, which increased to 26 Hz (0.43δ) at a molar ratio of 0.226. These large values, with relatively little lanthanide-induced line-broadening, should make possible the facile determination of optical purity of 1 even with a 60 MHz nmr spectrometer. Parallel studies were run using the achiral shift reagent, tris-(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium (III), 3, to confirm peak assignments. The considerable values of ΔΔδ may reflect the “soft base” character of the sulfur atom in 1. Less effective binding by sulfur to the lanthanide atom could lead to coordination by europium on the carbonyl oxygen, relatively close to the chiral center, providing enhanced AA5 values compared to some related compounds. While several other proton absorptions of 1 appear to show some observable ΔΔδ, they are less valuable for optical purity evaluation because of lower intensity, greater multiplicity, or small ΔΔδ value. The relative slopes of the plots of chemical shift, δ, for runs with 2 or 3, are consistent with the full assignment of the proton absorptions of 1 based on expected proximity of the protons to the complexed europium atom. The observed coupling constants of the vinyl hydrogens of 1 further support the assignments.

Determination of Sulfur in Rubber Vulcanizates

1956 ◽  
Vol 29 (2) ◽  
pp. 612-619 ◽  
Author(s):  
E. W. Zimmerman ◽  
V. E. Hart ◽  
Emanuel Horowitz
Keyword(s):  
Nitric Acid ◽  
Barium Sulfate ◽  
Combustion Method ◽  
Fusion Method ◽  
Total Sulfur ◽  
A Value ◽  
Acid Method ◽  
Barium Compounds ◽  
Good Agreement

Abstract A combustion method for rubber which determines the sulfur evolved at 480° to 500° C is compared with the fusion and the zinc-nitric acid methods. In the combustion method an interaction occurs between sulfur and fillers present in the rubber. The effect of particular fillers with respect to this interaction is discussed. A value representative of the organically bound sulfur in an extracted specimen can be obtained by the combustion method when no reaction takes place between the sulfur and the fillers during combustion. The fusion method yields results in good agreement with the total sulfur added in compounding the rubber samples. Except in the presence of barium compounds, the zinc-nitric acid method likewise determines total sulfur. When barium compounds are present, barium sulfate is formed during the oxidation, and low values are obtained for the total sulfur.

Vitamin A Value of Plant Food Provitamin A - Evaluated by the Stable Isotope Technologies

2014 ◽  
Vol 84 (Supplement 1) ◽  
pp. 25-29 ◽  
Author(s):  
Guangwen Tang
Keyword(s):  
Stable Isotope ◽  
Vitamin A ◽  
Provitamin A ◽  
Animal Origin ◽  
Plant Food ◽  
Plant Foods ◽  
A Value ◽  
Provitamin A Carotenoids ◽  
Β Carotene

Humans need vitamin A and obtain essential vitamin A by conversion of plant foods rich in provitamin A and/or absorption of preformed vitamin A from foods of animal origin. The determination of the vitamin A value of plant foods rich in provitamin A is important but has challenges. The aim of this paper is to review the progress over last 80 years following the discovery on the conversion of β-carotene to vitamin A and the various techniques including stable isotope technologies that have been developed to determine vitamin A values of plant provitamin A (mainly β-carotene). These include applications from using radioactive β-carotene and vitamin A, depletion-repletion with vitamin A and β-carotene, and measuring postprandial chylomicron fractions after feeding a β-carotene rich diet, to using stable isotopes as tracers to follow the absorption and conversion of plant food provitamin A carotenoids (mainly β-carotene) in humans. These approaches have greatly promoted our understanding of the absorption and conversion of β-carotene to vitamin A. Stable isotope labeled plant foods are useful for determining the overall bioavailability of provitamin A carotenoids from specific foods. Locally obtained plant foods can provide vitamin A and prevent deficiency of vitamin A, a remaining worldwide concern.

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