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The thermal dissociation reactions of C2F4 and C2F6 were studied in shock waves over the temperature range 1000-4000 K using UV absorption spectroscopy. Absorption cross sections of C2F4, CF2, CF, and C2 were derived and related to quantum-chemically modeled oscillator strengths. After confirming earlier results for the dissociation rates of C2F4, CF3, and CF2, the kinetics of secondary reactions were investigated. For example, the reaction CF2 + CF2 → CF + CF3 was identified. Its rate constant of 1010 cm3 mol-1 s-1 near 2400 K is markedly larger than the limiting high-pressure rate constant of the dimerization CF2 + CF2 → C2F4, suggesting that the reaction follows a different path. When the measurements of the thermal dissociation CF2 (+Ar) → CF + F (+Ar) are extended to temperatures above 2500 K, the formation of C2 radicals was shown to involve the reaction CF + CF → C2F + F (modeled rate constant 8.0 × 1012 (T/3500 K)1.0 exp(-4400 K/T) cm3 mol-1 s-1) and the subsequent dissociation C2F (+Ar) → C2 + F + (Ar) (modeled limiting low-pressure rate constant 3.0 × 1016 (T/3500 K)-4.0 exp(-56880 K/T) cm3 mol-1 s-1). This mechanism was validated by monitoring the dissociation of C2 at temperatures close to 4000 K. Temperature- and pressure-dependences of rate constants of reactions involved in the system were modeled by quantum-chemistry based rate theory.

The UV absorption spectrum of C2F5I was studied in shock waves over the temperature range 580–1200 K and, together with room temperature data, was represented in extended Sulzer–Wieland form. As a case study, the work illustrates the properties of high-temperature UV absorption continua for use in kinetics experiments in shock waves. A comparison with experimental data for CF3I and their representation is made. Quantum-chemical model calculations of positions and oscillator strengths are tested and, besides CF3I and C2F5I, applied also to spectra of C2F4I, C2F4, CF2I, C2F2, C2F, CF2, CFI, CF, and IF. Likewise, modelling and experimental results for the high-temperature UV absorption spectra of CF3 and C2F5 radicals are considered.

The thermal dissociation of Si(CH3)2F2 was studied in shock waves between 1400 and 1900 K. UV absorption-time profiles of its dissociation products SiF2 and CH3 were monitored. The reaction proceeds as a unimolecular process not far from the high-pressure limit. Comparing modelled and experimental results, an asymmetric representation of the falloff curves was shown to be most realistic. Modelled limiting high-pressure rate constants agreed well with the experimental data. The UV absorption spectrum of SiF2 was shown to be quasi-continuous, with a maximum near 222 nm and a wavelength-integrated absorption cross section of 4.3 (±1) × 10−23 cm3 (between 195 and 255 nm, base e), the latter being consistent with radiative lifetimes from the literature. Experiments over the range 1900–3200 K showed that SiF2 was not consumed by a simple bond fission SiF2 →SiF + F, but by a bimolecular reaction SiF2 + SiF2 → SiF + SiF3 (rate constant in the range 1011–1012 cm3 mol−1 s−1), followed by the unimolecular dissociation SiF3 → SiF2 + F such that the reaction becomes catalyzed by the reactant SiF2. The analogy to a pathway CF2 + CF2 → CF + CF3, followed by CF3 → CF2 + F, in high-temperature fluorocarbon chemistry is stressed. Besides the high-temperature absorption cross sections of SiF2, analogous data for SiF are also reported.

The thermal dissociation of C2F5I was studied in shock waves monitoring UV absorption signals from the reactant C2F5I and later formed reaction products such as CF, CF2, and C2F4. Temperatures of 950–1500 K, bath gas concentrations of [Ar] = 3 × 10−5–2 × 10−4 mol cm−3, and reactant concentrations of 100–500 ppm C2F5I in Ar were employed. Absorption-time profiles were recorded at selected wavelengths in the range 200–280 nm. It was found that the dissociation of C2F5I → C2F5 + I was followed by the dissociation C2F5 → CF2 + CF3, before the dimerization reactions 2CF2 → C2F4 and 2CF3 → C2F6 and a reaction CF2 + CF3 → CF + CF4 set in. The combination of iodine atoms with C2F5 and CF3 had also to be considered. The rate constant of the primary dissociation of C2F5I was analyzed in the framework of statistical unimolecular rate theory accompanied by a quantum-chemical characterization of molecular parameters. Rates of secondary reactions were modelled as well. Experimental rate constants for the dissociations of C2F5I and C2F5 agreed well with the modelling results. The comparably slow dimerization 2CF2 → C2F4 could be followed both by monitoring reactant CF2 and product C2F4 absorption signals, while CF3 dimerization was too fast to be detected. A competition between the dimerization reactions of CF2 and CF3, the recombination of CF2 and CF3 forming C2F5, and CF-forming processes like CF2 + CF3 → CF + CF4 finally was discussed.

The reaction of CF2 with H2 was studied in shock waves by monitoring UV absorption signals. CF2 was prepared by thermal dissociation of C2F4 (or of c-C3F6). The rate constant of the reaction CF2 + H2 → CHF + HF near 2000 K was found to be close to 1011 cm3 mol-1 s-1, consistent with earlier information on the reverse reaction CHF + HF → CF2 + H2 and a modeled equilibrium constant. The kinetic studies were accompanied by spectroscopic investigations. Absorption cross sections of C2F4 between 190 and 220 nm were measured near 1000 K and compared with room temperature values from the literature. Likewise, absorption cross sections of CF2 near 2000 K were measured between 210 and 300 nm and compared with room temperature data. Additional, superimposed, absorption signals were recorded during the reaction and identified by their time-dependence and by quantum-chemical calculations employing time-dependent density functional theory. A previously unknown absorption spectrum of CHF radicals near 200 nm was identi...

The unimolecular dissociation of CH2F2 leading to CF2 + H2, CHF + HF, or CHF2 + H is investigated by quantum-chemical calculations and unimolecular rate theory. Modeling of the rate constants is accompanied by shock wave experiments over the range of 1400–1800 K, monitoring the formation of CF2. It is shown that the energetically most favorable dissociation channel leading to CF2 + H2 has a higher threshold energy than the energetically less favorable one leading to CHF + HF. Falloff curves of the dissociations are modeled. Under the conditions of the described experiments, the primary dissociation CH2F2 → CHF + HF is followed by the reaction CHF + HF → CF2 + H2. The experimental value of the rate constant for the latter reaction indicates that it does not proceed by an addition–elimination process involving CH2F2* intermediates, as assumed before.

The thermal dissociation reaction CF

The thermal dissociation reaction CF3 (+ Ar) → CF2 + F (+ Ar) was studied in incident and reflected shock waves by monitoring UV absorption signals of the primary dissociation product CF2. CF3 radicals were produced by thermal decomposition of CF3I. Accounting for secondary reactions of F atoms, rate constants for the unimolecular dissociation were derived. Experimental parts of the falloff curves were obtained over the ranges 1544 - 2106 K and 1.0×〖10〗^(-5)≤["Ar" ]≤9.3×〖10〗^(-5 ) "mol " 〖"cm" 〗^"-3" . Theoretical modelling allowed for a construction of the full falloff curves connecting the limiting low pressure rate constants k_0=["Ar" ] 2.5×〖10〗^18 (T⁄(2000 "K" ))^(-5.1) " exp" ((-42450 "K" )⁄T) 〖"cm" 〗^"3" 〖"mol" 〗^(-1) "s" ^(-1) with the limiting high pressure rate constants k_∞= 1.6×〖10〗^16 (T⁄(2000 "K" ))^(-1.3) "exp" ((-43250 "K" )⁄T) "s" ^(-1) (center broadening factors of F_cent= 0.25, 0.22, and 0.20 at 1500, 2000, and 2500 K, respectively, were used). The influence of simplifications of falloff expressions and of limiting rate constants on the representation of experimental data is discussed.

The falloff curves of the unimolecular dissociation CF3I (+Ar) - CF3 + I (+Ar) are modelled by combining quantum-chemical characterizations of the potential energy surface for the reaction, standard unimolecular rate theory, and experimental information on the average energy transferred per collision between excited CF3I and Ar. The (essentially) parameter-free theoretical modelling gives results in satisfactory agreement with data deduced from earlier shock wave experiments employing a variety of reactant concentrations (between a few ppm and a few percent in the bath gas Ar). New experiments recording absorption–time signals of CF3I, I2, CF2 and (possibly) IF at 450–500 and 200–300 nm are reported. By analysing the decomposition mechanism, besides the unimolecular dissociation of CF3I, these provide insight into the influence of secondary reactions on the experimental observations. Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Sölter, L.. Universität Göttingen; Alemania Fil: Tellbach, E.. Universität Göttingen; Alemania Fil: Troe, J.. Universität Göttingen; Alemania. Institut Max Planck fuer Bioanorganische Chemie; Alemania

The thermal decomposition of perfluorotriethylamine, (C2F5)3N, was investigated in shock waves by monitoring the formation of CF2. Experiments were performed over the temperature range of 1120-1450 K with reactant concentrations between 100 and 1000 ppm of (C2F5)3N in the bath gas Ar and with [Ar] in the range of (0.7-5.5) × 10-5 mol cm-3. The experiments were accompanied by quantum-chemical calculations of the energies of various dissociation paths and by rate calculations, in particular for the dissociation of C2F5via C2F5 → CF3 + CF2. The overall reaction can proceed in different ways, either by a sequence of successive C-N bond ruptures followed by fast C2F5 decompositions, or by a sequence of alternating C-C and C-N bond ruptures. A cross-over between the two pathways can also take place. At temperatures below about 1300 K, yields of less than one CF2 per (C2F5)3N decomposed were observed. On the other hand, at temperatures around 2000 K, when besides the parent molecule, CF3 also dissociates, yields of six CF2 per (C2F5)3N decomposed were measured. The rate-delaying steps of the dissociation mechanism at intermediate temperatures were suggested to be the processes (C2F5)NCF2 → (C2F5)N + CF2 and (CF2)N → N + CF2. The reduction of the CF2 yields at low temperatures was tentatively attributed to a branching of the mechanism at the level of (C2F5)2NCF2, from where the cyclic final product perfluoro-N-methylpyrrolidine, (C4F8)NCF3, is formed which was identified in earlier work from the literature., Universidad Nacional de La Plata

The thermal unimolecular dissociation of CH3F was studied in shock waves by monitoring the UV absorption of a dissociation product identified as CH2F. It is concluded that, under conditions applied, the formation of this species corresponds to a minor, spin-allowed, dissociation channel of about 3% yield. Near to the low-pressure limit of the reaction, on the other hand, the energetically more favourable dissociation leads to 3CH2 + HF on a dominant, spin-forbidden, pathway. By considering the multichannel character of the reaction, it is shown that, in contrast to the low-pressure range, the high-pressure range of the reaction should be dominated by CH2F formation. The channel-switching probably takes place at pressures higher than those applied in the present work. In addition to the two dissociation channels of CH3F producing 3CH2 + HF and CH2F + H, a third, spin-allowed, dissociation channel leading to 1CHF + H2 was also considered and estimated to proceed with a yield smaller than 0.5%. Besides the dissociation of CH3F, the dissociation of CH2F was studied by monitoring the UV spectrum of CH2F. Details of this spectrum were investigated. Similar to CH3F, the dissociation of CH2F can proceed on several dissociation channels, under the present conditions either to CHF + H or to CF + H2. After modelling single-channel falloff curves for all reaction pathways, coupling effects of multichannel dissociations were interpreted in the framework of multichannel unimolecular rate theory.

The thermal dissociation of CH2F2 and the reaction of CF2 with H2 was studied in shock waves over the temperature range 1800–2200 K, monitoring the absorption–time profiles at 248 nm. Besides contributions from CF2, the signals showed strong absorptions from secondary reaction products, probably mostly CH2F formed by the reaction CHF + H2 → CH2F + H. Rate constants of a series of possible secondary reactions were modeled, including falloff curves for the thermal dissociations of CHF, CHF2, and CH2F and rate constants of the reactions CHF + CH2F2 → CHF2 + CH2F, CHF + H2 → CH2F + H, H + CH2F2 → CHF2 + H2, H + CF2 → CF + HF, and H + CF → C + HF. On this basis, concentration–time profiles were simulated and compared with experimental absorption–time profiles.

The reaction of CF

The unimolecular dissociation of CH

The thermal dissociation of C3F6 was studied between 1330 and 2210 K in shock waves monitoring the UV absorption of CF2. CF2 yields of about 2.6 per parent C3F6 were obtained at reactant concentrations of 500-1000 ppm in the bath gas Ar. These yields dropped to about 1.8 when reactant concentrations were lowered to 60 ppm. The increase of the CF2 yield with increasing concentration was attributed to bimolecular reactions between primary and secondary dissociation products. Quantum-chemical and kinetic modeling calculations helped to estimate the contributions from the various primary dissociation steps. It was shown that the measurements correspond to unimolecular reactions in their falloff range. Falloff representations of the rate constants are given, leading to an overall high pressure rate constant k∞ = 2.0 × 10(17)(-104 kcal mol(-1)/RT) s(-1) and a relative rate of about 2/3:1/3 for the reactions C3F6 → CF3CF + CF2 versus C3F6 → C2F3 + CF3. Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina Fil: Sölter, L.. Universitat of Gottingen; Alemania Fil: Tellbach, E.. Universitat of Gottingen; Alemania Fil: Troe, J.. Max-Planck-Institut für Biophysikalische Chemie; Alemania. Universitat of Gottingen; Alemania

The thermal decomposition of CF4 (+Ar) → CF3 + F (+Ar) was studied in shock waves over the temperature range 2000-3000 K varying the bath gas concentration [Ar] between 4 × 10(-6) and 9 × 10(-5) mol cm(-3). It is shown that the reaction corresponds to the intermediate range of the falloff curve. By combination with room temperature data for the reverse reaction CF3 + F (+He) → CF4 (+He) and applying unimolecular rate theory, falloff curves over the temperature range 300-6000 K are modeled. A comparison with the reaction system CH4 (+M) ⇔ CH3 + H (+M) is made.

This study was designed to investigate the use and impact of a continuous glucose monitoring system (the FreeStyle Navigator) under home-use conditions in the self-management of type 1 diabetes.A 20 day masked phase, when real-time data and alarms were not available, was compared with a subsequent 40 day unmasked phase for a number of specified measures of glycaemic variability. HbA(1c) (measured by DCA 2000) and a hypoglycaemia fear survey were recorded at the start and end of the study.The study included 48 patients with type 1 diabetes (mean age 35.7 +/- 10.9, range 18-61 years; diabetes duration 17.0 +/- 9.5 years). Two patients did not complete the study for personal reasons. Comparing masked (all 20 days) and unmasked (last 20 days) phases, the following reductions were seen: time outside euglycaemia from 11.0 to 9.5 h/day (p = 0.002); glucose SD from 3.5 to 3.2 mmol/l (p0.001); hyperglycaemic time (10.0 mmol/l) from 10.3 to 8.9 h/day (p = 0.0035); mean amplitude of glycaemic excursions (peak to nadir) down by 10% (p0.001); high blood glucose index down by 18% (p = 0.0014); and glycaemic risk assessment diabetes equation score down by 12% (p = 0.0013). Hypoglycaemic time (3.9 mmol/l) decreased from 0.70 to 0.64 h/day without statistical significance (p0.05). Mean HbA(1c) fell from 7.6 +/- 1.1% at baseline to 7.1 +/- 1.1% (p0.001). In the hypoglycaemia fear survey, the patients tended to take less snacks at night-time after wearing the sensor.Home use of a continuous glucose monitoring system has a positive effect on the self-management of diabetes. Thus, continuous glucose monitoring may be a useful tool to decrease glycaemic variability.

The thermal dissociation of octafluorocyclobutane, c-C4F8, was studied in shock waves over the range 1150-2300 K by recording UV absorption signals of CF2. It was found that the primary reaction nearly exclusively produces 2 C2F4 which afterwards decomposes to 4 CF2. A primary reaction leading to CF2 + C3F6 is not detected (an upper limit to the yield of the latter channel was found to be about 10 percent). The temperature range of earlier single pulse shock wave experiments was extended. The reaction was shown to be close to its high pressure limit. Combining high and low temperature results leads to a rate constant for the primary dissociation of k1 = 1015.97 exp(-310.5 kJ mol-1/RT) s-1 in the range 630-1330 K, over which k1 varies over nearly 14 orders of magnitude. Calculations of the energetics of the reaction pathway and the rate constants support the conclusions from the experiments. Also they shed light on the role of the 1,4-biradical CF2CF2CF2CF2 as an intermediate of the reaction., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

The thermal dissociation of c-C3F6 has been studied in shock waves over the range 620–1030 K monitoring the UV absorption of CF2. The reaction was studied close to its high-pressure limit, but some high-temperature falloff was accounted for. Quantum-chemical and kinetic modeling rationalized the experimental data. The reaction is suggested to involve the 1,3 biradical CF2CF2CF2 intermediate. CF2 formed by the dissociation of c-C3F6 dimerizes to C2F4. The measured rate of this reaction is also found to correspond to the falloff range. Rate constants for 2CF2 → C2F4 as a function of temperature and bath gas concentration [Ar] are given and shown to be consistent with literature values for the high-pressure rate constants from experiments at lower temperatures and dissociation rate constants obtained in the falloff range at higher temperatures. The onset of falloff at intermediate temperatures is analyzed. Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina Fil: Sölter, L.. Universitat of Gottingen; Alemania Fil: Tellbach, E.. Universitat of Gottingen; Alemania Fil: Troe, J.. Max-Planck-Institut für Biophysikalische Chemie; Alemania

The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400–2000 K and Ar bath gas concentrations in the range (2–10) × 10−5 mol cm−3 were employed. It is shown that the reactions are initiated by C–C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

The thermal dissociation reaction C2F4(+ M) → 2CF2(+ M) was studied in shock waves monitoring CF2 radicals by their UV absorption. The absorption coefficients as functions of wavelength and temperature were redetermined and are represented in analytical form. Dissociation rate constants as functions of bath gas concentration [M] and temperature, from previous and the present work, are presented analytically employing falloff expressions from unimolecular rate theory. Equilibrium constants are determined between 1200 and 1500 K. The data are shown to be consistent, with a C–C bond energy of 67.5 (±0.5) kcal mol–1. High-pressure limiting rate constants for dissociation and recombination are found to be unusually small. This phenomenon can be attributed to an unusually pronounced anisotropy of the potential energy surface, such as demonstrated by quantum-chemical calculations of the potential energy surface. Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina Fil: Croce, Adela Ester. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina Fil: Luther, K.. Universität Göttingen. Institut für Physikalische Chemie; Alemania Fil: Sölter, L.. Universität Göttingen. Institut für Physikalische Chemie; Alemania Fil: Tellbach, E.. Universität Göttingen. Institut für Physikalische Chemie; Alemania Fil: Troe, J.. Universität Göttingen. Institut für Physikalische Chemie; Alemania. Max-Planck-Institut für Biophysikalische Chemie; Alemania