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

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.

1979 ◽  
Vol 57 (12) ◽  
pp. 1468-1470 ◽  
Author(s):  
Stanley James W. Price ◽  
Henry J. Sapiano

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.


1973 ◽  
Vol 51 (22) ◽  
pp. 3662-3664 ◽  
Author(s):  
Michael J. Krech ◽  
Stanley James W. Price ◽  
Wayne F. Yared

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.


1977 ◽  
Vol 55 (24) ◽  
pp. 4222-4226 ◽  
Author(s):  
Michael J. Krech ◽  
Stanley James W. Price ◽  
Henry J. Sapiano

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).


1974 ◽  
Vol 52 (15) ◽  
pp. 2673-2678 ◽  
Author(s):  
Michael J. Krech ◽  
Stanley James W. Price ◽  
Wayne F. Yared

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.


2009 ◽  
Vol 60 (2) ◽  
pp. 147-156 ◽  
Author(s):  
Lida Bagdonienė ◽  
Danutė Labeikytė ◽  
Ivars Kalviņš ◽  
Veronika Borutinskaitė ◽  
Aleksandrs Prokofjevs ◽  
...  

Rat Serum Carboxylesterase Partly Hydrolyses Gamma-Butyrobetaine EstersAlthough described some time ago, gamma-butyrobetaine esters and related compounds have not gained much attention from researchers, and their physiological function remains obscure. Formerly we detected GBB-esterase enzymatic activity in rat blood serum using phenylated gamma-butyrobetaine as an artificial substrate of the enzyme and HPLC. The aim of the present work was to develop an assay that would enable spectrophotometric or colorimetric determination of the reaction products of GBB-esterase activity and to reveal individual proteins performing GBB-esterase activity in rat blood serum. For this purpose gamma-butyrobetaine 1-naphthyl ester was synthesised. Hydrolysis of this ester releases 1-naphthol, which increases the optical absorbance at 322 nm. We have shown that the enzymatic hydrolysis of GBB 1-naphthyl ester to 1-naphthol in rat blood serum is due to GBB-esterase activity. An attempt was done to purify the enzyme from rat blood serum. By combining DEAE Sepharose at pH 4.2 and affinity chromatography with procainamide we achieved a 68-fold enrichment of GBB-esterase activity in our preparations. Separation of fraction proteins in 2D protein electrophoresis with following mass-spectrometry indicated that GBB esterase activity in rat blood serum is performed in part by carboxylesterase.


2019 ◽  
Vol 57 (3) ◽  
pp. 93-98
Author(s):  
Svetlana E. Pratskova ◽  
◽  
Oksana E. Sirenko ◽  

Chlorination is a method of disinfection and oxidation of organic impurities in water. Chlorine is present in aqueous solutions in various forms, which are formed as a result of the chlorination of water. Spectrophotometric methods are very important for determining small amounts of chlorine and its compounds. The article presents a modification of the classical indophenolic method. Determination of active chlorine should be carried out at room temperature, maintaining the solutions for 50 minutes, the pH range is 11.9 ± 0.1. The optimal concentration of reagents: 33-fold excess of N-phenanthranilic acid, 2-fold excess of sodium nitroprusside, and the concentration of ammonium chloride should be 4 to 7 times less than the concentration of active chlorine. The following interaction scheme was proposed: oxidation of ammonia to chloramine with hypochlorite, amination of N-phenanthanilate with the formation of sodium 4-amino-N-phenylanthranilate, oxidation of 4-amino-N-phenylanthranilate with sodium hypochlorite to an indamin compound, followed by complexation with sodium nitroprusside. The linearity range of the calibration curve is 1-23 mg/l, the convergence is 2.3%, the relative error is 1%. The molar ratios of ions and oxidizing agents present in natural waters that do not interfere with the determination of active chlorine are investigated. The optimal concentrations of reagents, sequential variation of the concentration of solutions and fixing the change in light absorption were established. The ratio of the stoichiometric coefficients according to the reaction equation was: ammonium: N-phenanthranilic acid: sodium nitroprusside: hypochloride was 1: 2: 1: 1. It is proposed to use this method to determine the active chlorine in tap water. It is recommended to use the calibration schedule to determine the preliminary content, and to establish a more accurate concentration, use the method of additives.


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